Resist composition and pattern forming method using the same

ABSTRACT

A resist composition containing: a polymer having a group capable of decomposing under an action of an acid and having a weight average molecular weight of from 1,000 to 5,000, of which solubility in an alkali developer increases under an action of an acid; and a compound capable of generating a compound having a structure represented by the following formula (A-I) upon irradiation with actinic rays or radiation:
 
Q 1 -X 1 —NH—X 2 -Q 2   (A-I)
 
wherein Q 1  and Q 2  each independently represents a monovalent organic group, provided that either one of Q 1  and Q 2  has a proton acceptor functional group, Q 1  and Q 2  may be combined with each other to form a ring and the ring formed may have a proton acceptor functional group; and X 1  and X 2  each independently represents —CO— or —SO 2 —.

FIELD OF THE INVENTION

The present invention relates to a resist composition suitable for use in the ultramicrolithography process such as production of VLSI or high-capacity microchip or in other photofabrication processes. More specifically, the present invention relates to a resist composition capable of forming a high-resolution pattern by using electron beam, X-ray, EUV light or the like, that is, a resist composition suitably usable for ultrafine processing of a semiconductor device, where electron beam, X-ray or EUV light is used, and a pattern forming method using the resist composition.

BACKGROUND OF THE INVENTION

In the process of producing a semiconductor device such as IC and LSI, fine processing by lithography using a photoresist composition has been conventionally performed. Recently, with increase in the integration degree of an integrated circuit, formation of an ultrafine pattern in the sub-micron or quarter-micron region is being required. To cope with this requirement, the exposure wavelength also tends to become shorter, for example, from g line to l line or further to KrF excimer laser light.

At present, other than the excimer laser light, development of lithography using electron beam, X ray or EUV light is proceeding. Above all, the lithography using EUV light as a light source is positioned as a next-generation or next-next-generation promising pattern formation technique, and studies thereon are being aggressively made. The performances required of the resist used are high sensitivity, high resolution and good line edge roughness. However, these performances are in a trade-off relationship and it is important how to satisfy these performances at the same time. The line edge roughness as used herein means that the resist edge at the interface between the resist pattern and the substrate irregularly fluctuates in the direction perpendicular to the line direction due to the resist property and when the pattern is viewed from right above, the edge gives an uneven appearance. This unevenness is transferred by the etching step using the resist as a mask and causes deterioration of electric property, resulting in decrease in the yield, Particularly, in an ultrafine region of 0.25 μm or less, the improvement of line edge roughness is an essential problem to be solved. Such a problem is also important in the lithography using X-ray or electron beam.

As for the resist suitable for the lithography process using electron beam, X-ray or EUV light, a chemical amplification-type resist utilizing an acid catalytic reaction is mainly used from the standpoint of elevating the sensitivity and in conventional resists, there has been studied a chemical amplification-type resist composition mainly comprising an acid generator and a phenolic polymer which is insoluble or sparingly soluble in an aqueous alkali solution but becomes soluble in an aqueous alkali solution under the action of an acid. However, the conventional photoresist using a polymer compound for the substrate has a problem that the molecular shape of the polymer compound is reflected on the pattern profile or line edge roughness.

On the other hand, in the light of fine pattern formation and low line edge roughness, a low molecular material is recently attracting attention. In particular, a molecular resist using a simple molecule as the binder has been proposed, and there have been disclosed resist compositions using, for example, a phenol-based compound derivative having a specific structure (see, for example, JP-A-2003-183227 (the term “JP-A” as used herein means an “unexamined published Japanese patent application”) and JP-A-10-120610), a calixarene having a specific structure (see, for example, JP-A-10-120610 and JP-A-11-322656), a calixresorciarene (see, for example, JP-A-11-322656 and JP-A-2003-321423), or a phenol-based dendrimer with the mother nucleus being a calixresorcinarene (see, for example, JP-A-10-310545). A resist composition using a polyvalent phenol compound (JP-A-2005-266740) has been also disclosed.

However, it is pointed out that when such a molecular material is merely used, significant pattern falling occurs in the ultrafine region. An effective measure for solving this problem has not yet been found out.

SUMMARY OF THE INVENTION

An object of the present invention is to solve the problem by implementing performance-enhancing technology in the fine process of a semiconductor device, where active ray or radiation such as high energy ray, X-ray, electron beam and EUV light is used. In particular, the object of the present invention is to provide a resist composition in which a polymer with the weight average molecular weight being reduced in a constant amount is used as the low molecular compound expected to bring about high resolution in the ultrafine region and which thereby ensures that the problem of pattern falling found in the molecular resist in general is solved, high sensitivity and reduction in the line edge roughness (LER) are realized while maintaining the high resolution and reduced pattern falling, and good sensitivity and good dissolution contrast are achieved even in EUV exposure. The object of the present invention includes providing a pattern forming method using the resist composition.

The present invention is as follows.

The present inventors have made intensive studies, as a result, the above-described object is attained by a resist composition comprising a low molecular weight polymer having a group which produces an alkali-soluble group under the action of an acid, and a compound which generates a compound having a specific structure upon irradiation with actinic rays or radiation.

That is, the present invention is achieved by the following constructions.

(1) A resist composition comprising:

(B) a polymer having a group capable of decomposing under the action of an acid and having a weight average molecular weight of 1,000 to 5,000, of which solubility in an alkali developer increases under the action of an acid, and

(A) a compound capable of generating a compound having a structure represented by the following formula (A-I) upon irradiation with actinic rays or radiation: Q₁-X₁—NH—X₂-Q₂  (A-I) wherein Q₁ and Q₂ each independently represents a monovalent organic group, provided that either one of Q₁ and Q₂ has a proton acceptor functional group, Q₁ and Q₂ may be combined with each other to form a ring and the ring formed may have a proton acceptor functional group; and

X₁ and X₂ each independently represents —CO— or —SO₂—.

(2) The resist composition as described in (1), wherein the compound having a structure represented by formula (A-I) is a compound having a structure represented by the following formula (A-II): Q₁-X₁—NH—X₂-A-(X₃)_(n)-Q₃  (A-II) wherein Q₁ and Q₃ each independently represents a monovalent organic group, provided that either one of Q₁ and Q₃ has a proton acceptor functional group, Q₁ and Q₃ may be combined with each other to form a ring and the ring formed may have a proton acceptor functional group;

X₁, X₂ and X₃ each independently represents —CO— or —SO₂—;

A represents a divalent linking group;

B represents a single bond, an oxygen atom or —N(Q_(x))-;

Q_(x) represents a hydrogen atom or a monovalent organic group;

when B is —N(Q_(x))-, Q₃ and Q_(x) may be combined with each other to form a ring; and

n represents 0 or 1.

(3) The resist composition as described in (1) or (2), which comprises (7) a compound capable of generating an acid upon irradiation with actinic rays or radiation,

(4) The resist composition as described in any one of (1) to (3) above, which tier comprises a nitrogen-containing basic compound.

(5) The resist composition as described in any one of (1) to (4) above, which further comprises a surfactant.

(6) A pattern forming method comprising steps of forming a resist film from the resist composition described in any one of (1) to (5), and exposing and developing the resist film.

According to the present invention, a photosensitive composition realizing low line edge roughness and less occurrence of pattern failing, and a pattern forming method using the composition can be provided.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is described in detail below.

Incidentally, in the present invention, when a group (atomic group) is denoted without specifying whether substituted or unsubstituted, the group includes both a group having no substituent and a group having a substituent. For example, an “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The photosensitive composition, preferably the resist composition, of the present invention comprises (B) a polymer having a group capable of decomposing under the action of an acid and having a weight average molecular weight of 1,000 to 5,000, of which solubility in an alkali developer increases under the action of an acid, and (A) a compound capable of generating a compound having a structure represented by the following formula (A-I) upon irradiation with actinic rays or radiation.

[1] (B) Polymer Having a Group Capable of Decomposing Under the Action of an Acid and Having a Weight Average Molecular Weight of 1,000 to 5,000, of which Solubility in an Alkali Developer Increases Under the Action of an Acid (Hereinafter Sometimes Referred to as the “Component (B)”)

The resin capable of decomposing under the action of an acid to increase the solubility in an alkali developer (acid-decomposable resin), which is used in the photo-sensitive composition of the present invention, is a resin having a group capable of decomposing under the action of an acid (hereinafter sometimes referred to as an “acid-decomposable group”), in either one or both of the main chain and the side chain of the resin. Of these, a resin having an acid-decomposable group in the side chain is preferred.

The group capable of decomposing under the action of an acid is preferably a group resulting from replacement of the hydrogen atom of a —COOH or —OH group by a group which desorbs by the effect of an acid.

In the present invention, the acid-decomposable group is an acetyl group or a tertiary ester group.

In the resin for use in the present invention, the molar ratio between the alkali-soluble group and the acid-decomposable group contained in the resin is usually from 80/20 to 20/80, preferably from 70/30 to 30/70, more preferably from 60/40 to 40/60.

In the case where such a group capable of decomposing under the action of an acid is bonded as a side chain, the matrix resin is an alkali-soluble resin having an —OH or —COOH group in the side chain. Examples thereof include alkali-soluble resins described later.

The alkali dissolution rate of such an alkali-soluble resin is preferably 170 A/sec or more, more preferably 330 A/sec or more (A is angstrom), as measured (at 23° C.) in 0.261N tetramethylammonium hydroxide (TMAH).

From his standpoint, the alkali-soluble resin is preferably an alkali-soluble resin having a hydroxystyrene structural unit, such as o-, m- or p-poly(hydroxystyrene) or a copolymer thereof, hydrogenated poly(hydroxystyrene), halogen- or alkyl-substituted poly(hydroxystyrene), partially O-alkylated or O-acylated polyhydroxystyrene), styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer and hydrogenated novolak resin.

Preferred examples of the repeating unit having an acid-decomposable group for use in the present invention include a tert-butoxycarbonyloxystyrene, a 1-alkoxyethoxystyrene and a tertiary alkyl(meth)acrylate. Among these, a 2-alkyl-2-adamantyl(meth)acrylate and a dialkyl(1-adamantyl)methyl(meth)acrylate are more preferred.

The component (B) for use in the present invention can be obtained by reacting an acid-decomposable group precursor with an alkali-soluble resin or copolymerizing an acid-decomposable group-bonded alkali-soluble resin monomer with various monomers, and this is disclosed, for example, in European Patent 254853, JP-A-2-25850, JP-A-3-223860 and JP-A-4-251259.

In the case of irradiating the resist composition of the present invention with KrF excimer laser light electron beam, X-ray and high-energy beam at a wavelength of 50 mm or less (e.g., LTV), the resin as the component (B) preferably contains a repeating unit having an aromatic group, and the resin is more preferably (B1) a resin having a hydroxystyrene repeating unit, still more preferably a copolymer of hydroxystyrene/hydroxystyrene protected with an acid-decomposable group, or hydroxystyrene/tertiary alkyl(meth)acrylate.

In particular, the (B1) resin having a hydroxystyrene repeating unit is preferably a resin containing a repeating unit represented by the following formula (II) and a repeating unit represented by the following formula (III):

R₀₁ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.

L₁ and L₂, which may be the same or different, each represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aralkyl group,

M represents a single bond or a divalent linking group.

Q represents an alkyl group, a cycloalkyl group or an alicyclic or aromatic ring group which may contain a heteroatom.

At least two members out of Q, M and L₁ may combine to form a 5- or 6-membered ring.

A represents a halogen atom, a cyano group, an acyl group, an alkyl group, an alkoxy group, an acyloxy group or an alkoxycarbonyl group and is preferably an acyl group, an acyloxy group or an alkoxycarbonyl group, which are a group having a carbonyl group.

m and n each independently represents an integer of 0 to 4, provided that m and n are preferably not 0 at the same time.

The (B1) resin containing a hydroxystyrene repeating unit may be a resin containing a repeating unit represented by formula (II), a repeating unit represented by formula (III) and a repeating unit represented by formula (IV).

R₀₁ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.

B represents a halogen atom, a cyano group, an acyl group, an alkyl groups an alkoxy group, an acyloxy group or an alkoxycarbonyl group,

p represents an integer of 0 to 5.

The substituent on the benzene ring in the repeating unit represented by formula (II) is a group (acid-decomposable group) capable of decomposing under the action of an acid to generate a hydroxyl group (alkali-soluble group) and decomposes by the effect of an acid to produce a hydroxystyrene unit and convert the resin into a resin of which solubility in an alkali developer is increased.

R₀₁ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group and preferably has a carbon number of 20 or less.

The alkyl group or cycloalkyl group in R₀₁ preferably has a carbon number of 20 or less, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, an octyl group and a dodecyl group. These groups each may have a substituent, and examples of the substituent include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, an aralkylthio group, a thiophenecarbonyloxy group, a thiophenemethylcarbonyloxy group and a heterocyclic residue such as pyrrolidone residue. The substituent preferably has a carbon number of 8 or less. A CF₃ group, an alkoxycarbonylmethyl group, an alkylcarbonyloxymethyl group, a hydroxymethyl group, an alkoxymethyl group and the like awe more preferred.

The halogen atom in R₀₁ includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom and is preferably a fluorine atom.

As for the alkyl group contained in the alkoxycarbonyl group of R₀₁, the same as those described above for the alkyl group of R₀₁ are preferred.

The alkyl group of L₁ and L₂ is, for example, an alkyl group having a carbon number of 1 to 8, and specific preferred examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group and an octyl group.

The cycloalkyl group of L₁ and L₂ is, for example, a cycloalkyl group having a carbon number of 3 to 15, and specific preferred examples thereof include a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group.

The aryl group of L₁ and L₂ is, for example, an aryl group having a carbon number of 6 to 15, and specific preferred example thereof include a phenyl group, a tolyl group, a naphthyl group and an anthryl group.

The aralkyl group of L₁ and L₂ is, for example, an aralkyl group having a carbon number of 6 to 20, and examples thereof include a benzyl group and a phenethyl group.

The divalent linking group of M is, for example, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, —OCO—, —COO—, —CON(R₀)— or a linking group comprising a plurality of these members. R₀ is a hydrogen atom or an alkyl group.

The alkyl group and cycloalkyl group of Q are respectively the same as the alkyl group and cycloalkyl group of L₁ and L₂.

The alicyclic or aromatic ring group of Q, which may contain a heteroatom, includes, for example, the cycloalkyl group and aryl group of L₁ and L₂ and preferably has a carbon number of 3 to 15.

Examples of the alicyclic or aromatic ring group which may contain a heteroatom include thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole and pyrrolidone, but the alicyclic or aromatic ring group is not limited thereto and any ring may be used as long as it has a structure generally called a hetero ring (a ring formed by carbon and heteroatom or a ring formed by heteroatom).

As for the 5- or 6-membered ring which may be formed by combining at least two members out of Q, M and L₁, there is included a case where at least two members out of Q, M and L₁ combine to form, for example, a propylene group or a butylene group, thereby forming a 5- or 6-membered ring containing an oxygen atom.

The group represented by -M-Q preferably has a carbon number of 1 to 30, more preferably from 5 to 20, and, for example, the group represented by —OC(L₁)(L₂)O-M-Q includes the followings.

The acyl group of A is, for example, an acyl group having a carbon number of 2 to 8, and specific preferred examples thereof include a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group and a benzoyl group.

The alkyl group of A is, for example, an alkyl group having a carbon number of 1 to 8, and specific preferred examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group and an octyl group.

The alkoxy group of A is, for example, the above-described alkoxy group having a carbon number of 1 to 8, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group and a cyclohexyloxy group.

The acyloxy group or alkoxycarbonyl group of A includes groups corresponding to the above-described acyl group or alkoxy group.

These groups each may have a substituent, and preferred examples of the substituent include a hydroxyl group, a carboxyl group, a halogen atom (fluorine, chlorine, bromine, iodine) and an alkoxy group (e.g., methoxy, ethoxy, propoxy, butoxy). As for the cyclic structure, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 8).

m and n each independently represents an integer of 0 to 4. m and n each is preferably an integer of 0 to 2, more preferably 1.

Specific examples of the repeating unit represented by formula (II) are set forth below, but the present invention is not limited thereto.

Specific examples of the repeating unit represented by formula (III) are set forth below, but the present invention is not limited thereto.

R₀₁ in formula (IV) each independently represents a hydrogen atom an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group and preferably has a carbon number of 20 or less, and examples thereof are the same as those of R₀₁ in formula (II) or (III).

The acyl group, alkyl group, alkoxy group, acyloxy group and alkoxycarbonyl group of B in formula (IV) are the same as respective groups of A in formula (U).

p represents an integer of 1 to 5 and is preferably an integer of 0 to 2, more preferably 1.

Specific examples of the repeating unit represented by formula (IV) are set forth below, but the present invention is not limited thereto.

The resin (B) may contain a repeating unit represented by formula (V):

Ra to Rc each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group.

X₁ represents a hydrogen atom or an organic group.

The alkyl group of Ra to Rc is preferably an alkyl group having a carbon number of 1 to 5, and examples thereof include a methyl group, an ethyl group and a propyl group.

The organic group of X₁ preferably has a carbon number of 1 to 40 and may be an acid-decomposable group or a non-acid-decomposable group.

In the case of a non-acid-decomposable group, examples thereof are the same as those of die organic group in the non-acid-decomposable group of R₂ (since X₁ is an organic group, a halogen atom is not included). Other examples include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an alkyloxy group (excluding an —O— tertiary alkyl), an acyl group, a cycloalkyloxy group, an alkenyloxy group, a aryloxy group, an alkylcarbonyloxy group, an alkylamidomethyloxy group, an alkylamide group, an arylamidomethyl group and an arylamide group.

The non-acid-decomposable group is preferably an acyl group, an alkylcarbonyloxy group, an alkyloxy group, a cycloalkyloxy group, an aryloxy group, an alkylamideoxy group or an alkylamide group, more preferably an acyl group, an alkylcarbonyloxy group, an alkyloxy group, a cycloalkyloxy group or an aryloxy group.

In the non-acid-decomposable group, the alkyl group is preferably an alkyl group having a carbon number of 1 to 4, such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and tert-butyl group; the cycloalkyl group is preferably a cycloalkyl group having a carbon number of 3 to 10, such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group; the alkenyl group is preferably an alkenyl group having a carbon number of 2 to 4, such as vinyl group, propenyl group, allyl group and butenyl group; the aryl group is preferably an aryl group having a carbon number of 6 to 14, such as phenyl group, xylyl group, tolyl group, cumenyl group, naphthyl group and anthracenyl group; and the alkoxy group is preferably an alkoxy group having a carbon number of 1 to 4, such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy groups hydroxypropoxy group, n-butoxy group, isobutoxy group and sec-butoxy group.

Examples of the organic group of X₁, which is an acid-decomposable group, include —C(R_(11a))(R_(12a))(R_(13a)), —C(R_(14a))(R_(15a))(OR_(16a)) and —CO—OC(R_(11a))(R_(12a))(R_(13a)).

R_(11a) to R_(13a) each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group. R_(14a) and R_(15a) each independently represents a hydrogen atom or an alkyl group. R_(16a) represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group. Two members out of R_(11a), R_(12a) and R_(13a), or two members out of R_(14a), R_(15a) and R_(16a) may combine to form a ring.

Also, a group having an acid-decomposable group may be introduced into X₁ by modification. X₁ having introduced thereinto an acid-decomposable group is, for example, represented by the following formula: —[C(R_(17a))(R_(18a))]_(p)—CO—OC(R_(11a))(R_(12a))(R_(13a)) wherein R_(17a) and R_(18a) each independently represents a hydrogen atom or an alkyl group, and p represents an integer of 1 to 4.

The organic group of X₁ is preferably an acid-decomposable group having at least one cyclic structure selected from an alicyclic structure, an aromatic cyclic structure and a crosslinked alicyclic structure, and preferably has a structure containing an aromatic group (particularly phenyl group) or a structure containing an alicyclic or crosslinked alicyclic structure represented by any one of the following formulae (pI) to (pVI):

In formulae, R₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl groups an n-butyl group, an isobutyl group or a sec-butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with the carbon atom.

R₁₂ to R₁₆ is each independently represents a linear or branched alkyl group having a carbon number of 1 to 4 or an alicyclic hydrocarbon group, provided that at least one of R₁₂ to R₁₄ or either one of R₁₅ and R₁₆ represents an alicyclic hydrocarbon group.

R₁₇ to R₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having a carbon number of 1 to 4 or an alicyclic hydrocarbon group, provided that at least one of R₁₇ to R₂₁ represents an alicyclic hydrocarbon group and that either one of R₁₉ and R₂₁ represents a linear or branched alkyl group having a carbon number of 1 to 4 or an alicyclic hydrocarbon group.

R₂₂ to R₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having a carbon number of 1 to 4 or an alicyclic hydrocarbon group, provided that at least one of R₂₂ to R₂₅ represents an alicyclic hydrocarbon group, ad R₂₃ and R₂₄ may combine with each other to form a ring.

In formulae (pI) to (pVI), the alkyl group of R₁₂ to R₂₅ is a linear or branched alkyl group having a carbon number of 1 to 4, which may be substituted or unsubstituted, and examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.

Examples of the substituent which the alkyl group may further have include an alkoxy group having a carbon number of 1 to 4, a halogen atom (fluorine, chlorine, bromine, iodine), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, a carboxy group, an alkoxycarbonyl group and a nitro group.

The alicyclic hydrocarbon group of R₁₁ to R₂₅ and the alicyclic hydrocarbon group formed by Z together with the carbon atom may be monocyclic or polycyclic. Specific examples thereof include a group having a carbon number of 5 or more and having a monocyclo, bicyclo, tricyclo or tetracyclo structure. The carbon number thereof is preferably from 6 to 30, more preferably from 7 to 25. These alicyclic hydrocarbon groups each may have a substituent.

Examples of the structure of the alicyclic moiety in the alicyclic hydrocarbon group are set forth below.

Among these alicyclic moieties, preferred in the present invention art an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group and a cyclododecanyl group, more preferred are an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group and a cyclododecanyl group.

Examples of the substituent which the alicyclic hydrocarbon group may have include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, more preferably a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group and an isopropyl group. Examples of the alkoxy group include an alkoxy group having from a carbon number of 1 to 4, such as methoxy group, ethoxy group, propoxy group and butoxy group.

The alkyl group, alkoxy group and alkoxycarbonyl group each may further have a substituent, and examples of the substituent include an alkoxy group having a carbon number of 1 to 4 (e.g., methoxy, ethoxy, butoxy), a hydroxy group, an oxo group, an alkylcarbonyl group (preferably having a carbon number of 2 to 5), an alkylcarbonyloxy group (preferably having a carbon number of 2 to 5), an alkyloxycarbonyl group (preferably having a carbon number of 2 to 5) and a halogen atom (e.g., chlorine, bromine, fluorine).

In the resin (B), for maintaining good developability with an alkali developer, another appropriate polymerizable monomer may be copolymerized so that an alkali-soluble group such as phenolic hydroxyl group, carboxyl group, sulfonic acid group and hexafluoroisopropanol group (—C(CF₃)₂H) can be introduced, or for enhancing the film property, another hydrophobic polymerizable monomer such as alkyl acrylate and alkyl methacrylate may be copolymerized.

The content of the repeating unit represented by formula (II) is preferably from 5 to 60 mol %, more preferably from 10 to 50 mol %, still more preferably from 10 to 40 mol %, based on all repeating units constituting the resin.

The content of the repeating unit represented by formula (III) is preferably from 40 to 90 mol %, more preferably from 45 to 80 mol %, still more preferably from 50 to 75 mol %, based on all repeating units constituting the resin.

The content of the repeating unit represented by formula (IV) is preferably from 5 to 50 mol %, more preferably from 10 to 40 mol %, still more preferably from 15 to 30 mol %, based on all repeating units constituting the resin.

The content of the repeating unit represented by formula (V) is preferably form 0 to 30 mol %, more preferably from 0 to 20 mol %, still more preferably from 0 to 10 mol %, based on all repeating units constituting the resin.

The content of the repeating unit having an alkali-soluble group such as hydroxyl group, carboxy group and sulfonic acid group is preferably from 1 to 99 mol %, more preferably from 3 to 95 mol %, still more preferably from 5 to 90 mol %, based on all repeating units constituting the resin.

The content of the repeating unit having an acid-decomposable group is preferably from 3 to 95 mol %, more preferably from 5 to 90 mol %, still more preferably from 10 to 85 mol %, based on all repeating units constituting the resin.

The weight average molecular weight of the resin (B1) is, as a polystyrene-reduced value by the GPC method, from 1,000 to 5,000, preferably from 1,500 to 4,000, more preferably from 2,000 to 3,000. When the weight average molecular weight is 1,000 or more, the performance in terms of collapse is enhanced, and when it is 5,000 or less, the performance in terms of sensitivity, resolution and LER is enhanced.

The dispersity (Mw/Mn) of the resin (B1) is preferably from 1.0 to 3.0, more preferably from 1.05 to 2.0, still more preferably from 1.1 to 1.7.

As for the resin (B1), two or more kinds of resins may be used in combination.

Specific examples of the resin (B1) are set forth below, but the present invention is not limited thereto.

In these specific examples, “tBu” indicates a tert-butyl group.

The content of the group capable of decomposing under the action of an acid is expressed by B/(B+S) using the number (B) of acid-decomposable groups in the resin and the number (S) of alkali-soluble groups not protected by a group which desorbs by the effect of an acid. The content is preferably from 0.01 to 0.7, more preferably from 0.05 to 0.50, still more preferably from 0.05 to 0.40.

Also, the resin as the component (B) may be a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure and undergoing decomposition under the action of an acid to increase the solubility in an alkali developer.

The resin having a monocyclic or polycyclic alicyclic hydrocarbon structure and undergoing decomposition under the action of an acid to increase the solubility in an alkali developer (hereinafter sometimes referred to as an “alicyclic hydrocarbon-based acid-decomposable resin”) is preferably a resin containing at least one repeating unit selected from the group consisting of a repeating unit having an alicyclic hydrocarbon-containing partial structure represented by any one of the following formulae (pI) to (pVI), and a repeating unit represented by the following formula (II-AB):

In formulae (pI) to (pVI), R₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z represents an atomic group necessary for forming a cycloalkyl group together with the carbon atom.

R₁₂ to R₁₆ each independently represents a linear or branched alkyl group having a carbon number of 1 to 4 or a cycloalkyl group, provided that at least one of R₁₂ to R₁₄ or after one of R₁₅ and R₁₆ represents a cycloalkyl group.

R₁₇ to R₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having a carbon number of 1 to 4 or a cycloalkyl group, provided that at least one of R₁₇ to R₂₁ represents a cycloalkyl group and that either one of R₁₉ and R₂₁ represents a linear or branched alkyl group having a carbon number of 1 to 4 or a cycloalkyl group.

R₂₂ to R₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having a carbon number of 1 to 4 or a cycloalkyl group, provided that at least one of R₂₂ to R₂₅ represents a cycloalkyl group, R₂₃ and R₂₄ may be combined with each other to form a ring.

In formula (II-AB), R₁₁′ and R₁₂′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.

Z′ represents an atomic group for forming an alicyclic structure including the two bonded carbon atoms (C—C).

Formula (II-AB) is preferably the following formula (II-A) or (II-B):

In formulae (II-A) and (II-B), R₁₃′ to R₁₆′ each independently represents a hydrogen atom, a halogen atom, a cyano group, —COOH—, —COOR₅, a group capable of decomposing under the action of an acid, —C(═O)—X-A′-R₁₇′, an alkyl group or a cycloalkyl group.

R₅ represents an alkyl group, a cycloalkyl group or a —Y group shown below.

X represents an oxygen atom, a sulfur atom, —N—, —NHSO₂ or —NHSO₂NH—.

A′ represents a divalent linking group.

At least two members out of R₁₃′ to R₁₆′ may be combined to form a ring. n represents 0 or 1.

R₁₇′ represents —COOH—, COOR₅, —CN, a hydroxyl group, an alkoxy group, —CO—NH—R₆, —CO—NH—SO₂—R₆ or a —Y group shown below.

R₆ represents an alkyl group or a cycloalkyl group.

—Y Group:

In the —Y group, R₂₁′ to R₃₀′ each independently represents a hydrogen atom or an alkyl group, and a and b each represents 1 or 2.

In formulae (pI) to (pVI), the alkyl group of R₁₂ to R₂₅ is a linear or branched alkyl group having a carbon number of 1 to 4, and examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.

Examples of the substituent which the alkyl group and alkoxy group may have include an alkoxy group having a carbon number of 1 to 4, a halogen atom (e.g., fluorine, chlorine, bromine, iodine), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, a carboxy group, an alkoxycarbonyl group and a nitro group.

The cycloalkyl group of R₁₁ to R₂₅ and the cycloalkyl group fanned by Z together with the carbon atom may be monocyclic or polycyclic. Specific examples thereof include a group having a monocyclo, bicyclo, tricyclo or tetracyclo structure with a carbon number of 5 or more. The carbon number thereof is preferably from 6 to 30, more preferably from 7 to 25. These cycloalkyl groups each may have a substituent.

Preferred examples of the cycloalkyl group include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group and a cyclododecanyl group. Among these, an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group and a cyclodecanyl group are more preferred.

Examples of the substituent for such a cycloalkyl group include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and is more preferably selected from the group consisting of a methyl group, an ethyl group, a propyl group and an isopropyl group. The alkoxy group includes an alkoxy group having a carbon number of 1 to 4, such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the substituent which the alkyl group, alkoxy group, alkoxycarbonyl group and the like may further have include a hydroxyl group, a halogen atom and an alkoxy group.

The structures represented by formulae (pI) to (pVI) each can be used for the protection of an alkali-soluble group in the resin. Examples of the alkali-soluble group include various groups known in this technical field.

Specific examples thereof include a carboxylic acid group, a sulfonic acid group, a phenol group and a thiol group, with a carboxylic acid group and a sulfonic acid group being preferred.

Preferred examples of the alkali-soluble group protected by the structure represented by any one of formulae (pI) to (pVI) in the resin include structures where a hydrogen atom of a carboxyl group is substituted by the structure represented by any one of formulae (pI) to (pVI).

The repeating unit having an alkali-soluble group protected by the structure represented by any one of formulae (pI) to (pVI) is preferably a repeating unit represented by the following formula (pA).

In the formula, R represents a hydrogen atom, a halogen atom or a linear or branched alkyl group having from 1 to 4 carbon atoms, and a plurality of R's may be the same or different.

A represents a single bond, or a solo group or a combination of two or more groups, selected from the group consisting of an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amido group, a sulfonamido group, a urethane group and a urea group.

Ra represents any one group of formulae (pI) to (pVI).

The repeating unit represented by formula (pA) is most preferably a repeating unit comprising a 2-alkyl-2-adamantyl(meth)acrylate or a dialkyl(1-adamantyl)methyl (meth)acrylate.

Specific examples of the repeating unit represented by formula (pA) are set forth below.

(In formulae, Rx is H, CH₃ or CF₃.)

In formula (II-AB), R₁₁′ and R₁₂′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.

Z′ represents an atomic group for forming an alicyclic structure including the two bonded carbon atoms (C—C).

Examples of the halogen atom of R₁₁′ and R₁₂′ include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom.

The alkyl group of R₁₁′, R₁₂′ and R₂₁′ to R₃₀′ is preferably a linear or branched alkyl group having a carbon number of 1 to 10, more preferably a linear or branched alkyl group having a carbon number of 1 to 6, still more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group.

Examples of the substituent which the all group may mer have include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom; examples of the alkoxy group include an alkoxy group having a carbon number of 1 to 4, such as methoxy group, ethoxy group, propoxy group and butoxy group; examples of the acyl group include a formyl group and an acetyl group; and examples of the acyloxy group include an acetoxy group.

The atomic group for forming an alicyclic structure, represented by Z′, is an atomic group for forming a repeating unit of alicyclic hydrocarbon which may have a substituent, in the resin Sand among these atomic groups, an atomic group for forming a crosslinked alicyclic structure t form a crosslinked alicyclic hydrocarbon repeating unit is preferred.

Examples of the skeleton of alicyclic hydrocarbon formed are the same as those of the alicyclic hydrocarbon group of R₁₁ to R₂₅ in formulae (pI) to (pVI).

The alicyclic hydrocarbon skeleton may have a substituent, and examples of the substituent include R₁₃′ to R₁₆′ in formulae (II-A) and (II-B).

Among the repeating units having a crosslinked alicyclic hydrocarbon, the repeating units represented by formulae (II-A) and (II-B) are more preferred.

In the alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention, the acid-decomposable group may be contained in the —C(═O)—X-A′-R₁₇′ or may be contained as a substituent of Z′ in formula (II-AB).

The structure of the acid-decomposable group is represented by —C(—O)—X₁—R₀.

In this formula, R₀ represents a tertiary alkyl group such as tertbutyl group and tert-amyl group, an isoboronyl group, a 1-alkoxyethyl group such as 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group and 1-cyclohexyloxyethyl group, an alkoxymethyl group such as 1-methoxymethyl group and 1-ethoxymethyl group, a 3-oxoalkyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a trialkylsilylester group, a 3-oxocyclohexylester group, a 2-methyl-2-adamantyl group, a mevalonic lactone residue or the like, and X₁ has the same meaning as X above.

Examples of the halogen atom of R₁₃′ to R₁₆′ include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom.

The alkyl group of R₅, R₆ and R₁₃′ to R₁₆′ is preferably a linear or branched alkyl group having a carbon number of 1 to 10, more preferably a linear or branched alkyl group having a carbon number of 1 to 6, still more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group.

The cycloalkyl group of R₅, R₆ and R₁₃′ to R₁₆′ is, for example, a monocyclic alkyl group or a crosslinked hydrocarbon, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, all adamantyl group, a 2-methyl-2-adamantyl group, a norbornyl group, a boronyl group, an isoboronyl group, a tricyclodecanyl group, a dicyclopentenyl group, a norbornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group and a tetracyclododecanyl group.

The ring formed resulting from at least two members out of R₁₃′ to R₁₆′ being combined includes a ring having a carbon number of 5 to 12, such as cyclopentene, cyclohexene, cycloheptane and cyclooctane.

The alkoxy group of R₁₇′ includes an alkoxy group having a carbon number of 1 to 4, such as methoxy group, ethoxy group, propoxy group and butoxy group.

Examples of the substituent which the alkyl group, cycloalkyl group and alkoxy group may further have include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group, an alkyl group and a cycloalkyl group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom; examples of the alkoxy group include an alkoxy group having a carbon number of 1 to 4, such as methoxy group, ethoxy group, propoxy group and butoxy group; examples of the acyl group include a formyl group and an acetyl group; and examples of the acyloxy group include an acetoxy group.

Examples of the alkyl group and cyclic hydrocarbon group include those described above.

The divalent linking group of A′ includes a sole group or a combination of two or more groups, selected from the group consisting of an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an ado group, a sulfonamido group, a urethane group and a urea group.

In the alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention, the group capable of decomposing under the action of an acid may be contained in at least one repeating unit out of the repeating unit having an alicyclic hydrocarbon-containing partial structure represented by any one of formulae (pI) to (pVI), the repeating unit represented by formula (II-AB), and the repeating unit of a copolymerization component which is described later.

Various substituents R₁₃′ to R₁₆′ in formulae (II-A) and (II-B) may become the substituents of an atomic group for forming an alicyclic structure in formula (II-AB) or an atomic group Z for forming a crosslinked alicyclic structure.

Specific examples of the repeating units represented by formulae (II-A) and (II-B) are set forth below, but the present invention is not limited to these specific examples.

The alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention preferably has a lactone group, more preferably a repeating unit containing a group having a lactone structure represented by the following formula (Lc) or by any one of the following formulae (V-1) to (V-5). Also, the group having a lactone structure may be bonded directly to the main chain.

In formula (Lc), Ra₁, Rb₁, Rc₁, Rd₁ and Re₁ each independently represents a hydrogen atom or an alkyl group, m and n each independently represents an integer of 0 to 3, and m+n is from 2 to 6.

In formulae (V-1) to (V-5), R_(1b) to R_(5b) each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylsulfonylimino group or an alkenyl group, and two members out of R_(1b) to R_(5b) may be combined to form a ring.

The alkyl group of Ra₁ to Re₁ in formula (Lc) and the alkyl group in the alkyl group, alkoxy group, alkoxycarbonyl group and alkylsulfonylimino group of R_(1b) to R_(5b) in formulae (V-1) to (V-5) include a linear or branched alkyl group and may have a substituent. Preferred examples of the substituent which the alkyl group may have include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group and a cycloalkyl group.

Examples of the repeating unit containing a group having a lactone structure represented by formula (La) or by any one of formulae (V-1) to (V-5) include a repeating unit where at least one of R₁₃′ to R₁₆′ in formula (II-A) or (II-B) ha a group represented by formula (Lc) or by any one of formulae (V-1) to (V-5) (for example, when R₅ of —COOR₅ is a group represented by formula (Lc) or by any one of formulae (V-1) to (V-5)), and a repeating unit represented by the following formula (AI):

In formula (AI), R_(b0) represents a hydrogen atom, a halogen atom or an alkyl group having a carbon number of 1 to 4. Preferred examples of the substituent which the alkyl group of R_(b0) may have include those described above as preferred examples of the substituent which the alkyl group of R_(1b) in formulae (V-1) to (V-5) may have.

Examples of the halogen atom of R_(b0) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R_(b0) is preferably a hydrogen atom.

A′ represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group or a divalent group comprising a combination thereof.

B₂ represents a group represented by formula (Lc) or by any one of formulae (V-1) to (V-5).

Specific examples of the repeating unit containing a group having a lactone structure are set forth below, but the present invention is not limited thereto.

(In formulae, Rx is H, CH₃ or CF₃.)

(In formulae, Rx is H, CH₃ or CF₃.)

(In formulae, Rx is H, CH₃ or CF₃.)

The alicyclic hydrocarbon-based acid-decomposable rosin for use in the present invention may have a repeating unit containing a group having an adamantane skeleton represented by the following formula (VII):

In formula (VII), R_(2c) to R_(4c) each independently represents a hydrogen atom or a hydroxyl group, provided that at least one of R_(2c) to R_(4c) represents a hydroxyl group.

The group represented by formula (VII) is preferably a dihydroxy form or a monohydroxy form more preferably a dihydroxy form.

Examples of the repeating unit having a group represented by formula (VII) include a repeating unit where at least one of R₁₃′ to R₁₆′ in formula (II-A) or (II-B) has a group represented by formula (VII) (for example, when R₅ in —COOR₅ is a group represented by formula (VII)), and a repeating unit represented by the following formula (AII):

In formula (AII), R_(1c) represents a hydrogen atom or a methyl group.

R_(2c) to R_(4c) each independently represents a hydrogen atom or a hydroxyl group, provided that at least one of R_(2c) to R_(4c) represents a hydroxyl group. A repeating unit where two members out of R_(2c) to R_(4c) are a hydroxyl group is preferred.

Specific examples of the repeating unit having the structure represented by formula (AII) are set forth below, but the present invention is not limited thereto.

The alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention may contain a repeating unit represented by the following formula (VIII):

In formula (VIII), Z₂ represents —O— or —N(R₄₁)—, R₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group or —OSO₂—R₄₂, and R₄₂ represents an alkyl group, a cycloalkyl group or a camphor residue. The alkyl group of R₄₁ and R₄₂ may be substituted by a halogen atom preferably fluorine atom) or the like.

Specific examples of the repeating unit represented by formula (VIII) are set forth below, but the present invention is not limited thereto.

The alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention preferably contains a repeating unit having an alkali-soluble group, more preferably a repeating unit having a carboxyl group. By virtue of containing such a repeating unit, the resolution increases in usage of forming contact holes. As for the repeating unit having a carboxyl group, a repeating unit where a carboxyl group is directly bonded to the resin main chain, such as repeating unit by an acrylic acid or a methacrylic acid, and a repeating unit where a carboxyl group is bonded to the resin main chain through a linking group, both are preferred. The linking group may have a monocyclic or polycyclic hydrocarbon structure. An acrylic acid and a methacrylic acid are most preferred.

The alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention may contain, in addition to the above-described repeating units, various repeating structural units for the purpose of controlling the dry etching resistance, suitability for standard developer, adhesion to substrate, resist profile and properties generally required of the resist, such as resolving power, heat resistance and sensitivity.

Examples of such repeating structural units include repeating structural units corresponding to the monomers described below, but the present invention is not limited thereto.

By containing these repeating structural units, the performances required of the alicyclic hydrocarbon-based acid-decomposable resin, particularly, (1) solubility in the coating solvent, (2) film-forming property (glass transition point), (3) alkali developability, (4) film loss (selection of hydrophilic, hydrophobic or alkali-soluble group), (5) adhesion of unexposed area to substrate, (6) dry etching resistance, and the like can be subtly controlled.

Examples of the monomer include compounds having one addition polymerizable unsaturated bond, selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers and vinyl esters.

Other than these, an addition polymerizable unsaturated compound copolymerizable with the monomer corresponding to the above-described various repeating structural units may be copolymerized.

In the alicyclic hydrocarbon-based acid-decomposable resin, the molar ratio of each repeating structural unit contained is appropriately determined to control the dry etching resistance of resist, suitability for standard developer, adhesion to substrate, resist profile and performances generally required of the resist, such as resolving power, heat resistance and sensitivity.

Preferred embodiments of the alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention include:

(1) a resin containing a repeating unit having an alicyclic hydrocarbon-containing partial structure represented by any one of formulae (pI) to (pVI) (side chain type), and

(2) a resin containing a repeating unit represented by formula (II-AB) (main chain type).

The resin of (2) further includes, for example,

(3) a resin having a repeating unit represented by formula (II-AB), a maleic anhydride derivative and a (meth)acrylate structure (hybrid type).

In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit having an acid-decomposable group is preferably from 10 to 60 mol %, more preferably from 20 to 50 mol %, still more preferably from 25 to 40 mol %, based on all repeating structural units.

In the present invention, at least one methacrylic acid ester repeating unit and at least one acrylic aid ester repeating unit we preferably contained as the repeating unit having an acid-decomposable group. The molar ratio between the acrylic acid ester and the methacrylic acid ester is generally from 10/90 to 90/10 preferably from 20/80 to 80/20, more preferably from 30170 to 70/30, and most preferably from 40160 to 60/40.

In the alicyclic hydrocarbon-based acid-decomposable resins the content of the repeating unit having an alicyclic hydrocarbon-containing partial structure represented by any one of formulae (pI) to (pVI) is preferably from 30 to 70 mot %, more preferably from 35 to 55 mol %, still more preferably from 40 to 60 mol %, based on all repeating structural units.

In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit represented by formula (II-AB) is preferably from 0 to 60 mol %, more preferably from 15 to 55 mol %, still more preferably from 20 to 50 mol %, based on all repeating structural units.

The content of the repeating structural unit based on the monomer as the further copolymerization component in the resin can also be appropriately selected according to the desired resist performance, but the content thereof is preferably 99 mol % or less, more preferably 90 mol % or less, still more preferably 80 mol % or less, based on the total molar number of the repeating structural unit having an alicyclic hydrocarbon-containing partial structure represented by any one of formulae (pI) to (pVI) and the repeating unit represented by formula (II-AB).

The alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention can be synthesized by an ordinary method (for example, radical polymerization). For example, in a general synthesis method, the monomer species are charged into a reaction vessel en bloc or in the course of reaction and dissolved, if desired, in a reaction solvent such as tetrahydrofuran, 1,4-dioxane, ethers (e.g., diisopropyl ether) and ketones (e.g., methyl ethyl ketone, methyl isobutyl ketone), an ester solvent such as ethyl acetate, or a solvent capable of dissolving the composition of the present invention, such as propylene glycol monomethyl ether acetate described later, to prepare a uniform solution, and the polymerization is then initiated using a commercially available radical initiator (e.g., azo-based initiator, peroxide) in an inert gas atmosphere such as nitrogen or argon under heating, if desired. The initiator is added additionally or in parts, if desired. After the completion of reaction, the reactant is charged into a solvent, and the desired polymer is recovered by a method such as powder or solid recovery. The reaction concentration is 20 mass % or more, preferably 30 mass % or more, still more preferably 40 mass % or more, and the reaction temperature is from 10 to 150° C., preferably from 30 to 120° C., more preferably from 50 to 100° C.

In the photosensitive composition of the present invention, it is usually preferred that the component B has an acid-decomposable group having a carbon number of 4 or more, more preferably 10 or more, still more preferably 12 or more.

[2] (A) Compound Capable of Generating a Compound Having a Structure Represented by the Following Formula (A-I) Upon Irradiation with Actinic Rays or Radiation (Hereinafter Sometimes Referred to as the “Compound (A)”) Q₁-X₁—NH—X₂-Q₂  (A-I)

In formula (A-I), Q₁ and Q₂ each independently represents a monovalent organic group, provided that either one of Q₁ and Q₂ has a proton acceptor functional group, Q₁ and Q₂ may be combined with each other to form a ring, and the ring formed may have a proton acceptor functional group.

X₁ and X₂ each independently represents —CO— or —SO₂—.

The monovalent organic group as Q₁ and Q₂ in formula (A-I) is preferably a monovalent organic group having a carbon number of 1 to 40, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group. In the case where a proton acceptor functional group is present, the proton acceptor functional group may be present at the terminal, in the chain or as a side chain of the monovalent organic group such as alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group.

The alkyl group of Q₁ and Q₂, which may further have a substituent, is preferably a linear or branched alkyl group having a carbon number of 1 to 30 and may contain an oxygen atom, a sulfur atom or a nitrogen atom in the alkyl chain. Specific examples thereof include a linear alkyl group such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group and n-octadecyl group; and a branched alkyl group such as isopropyl group, isobutyl group, tert-butyl group, neopentyl group ad 2-ethylhexyl group.

The cycloalkyl group of Q₁ and Q₂ which may further have a substituent, is preferably a cycloalkyl group having a carbon number of 3 to 20 and may contain an oxygen atom or a nitrogen atom in the ring. Specific examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group.

The aryl group of Q₁ and Q₂, which may further have a substituent, is preferably an aryl group having a carbon number of 6 to 14, and examples thereof include a phenyl group and a naphthyl group.

The aralkyl group of Q₁ and Q₂, which may further have a substituent, is preferably an aralkyl group having a carbon number of 7 to 20, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group and a naphthylethyl group.

The alkenyl group of Q₁ and Q₂, which may further have a substituent, includes a group having a double bond at an arbitrary position of the alkyl group above.

Examples of the substituent which these groups each may further have include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having a carbon number of 3 to 10), an aryl group (preferably having a carbon number of 6 to 14), an alkoxy group (preferably having a carbon number of 1 to 10), an acyl group (preferably having a carbon number of 2 to 20), an acyloxy group (preferably having a carbon number of 2 to 10), an alkoxycarbonyl group (preferably having a carbon number of 2 to 20), and an aminoacyl group (preferably having a carbon number of 2 to 10).

As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 10). As for the aminoacyl group, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 10). Examples of the alkyl group having a substituent include a perfluoroalkyl group such as perfluoromethyl group, perfluoroethyl group perfluoropropyl group and perfluorobutyl group.

Either one monovalent organic group of Q₁ an Q₂ has a proton acceptor functional group. The proton acceptor functional group is a group capable of electrostatically interacting with a proton or a functional group having a lone pair of electrons, and examples thereof include a functional group having a microcyclic structure such as cyclic polyether, and a functional group containing a nitrogen atom having a lone pair of electrons less contributing to n-conjugation. Examples of the nitrogen atom having a lone pair of electrons less contributing to n-conjugation include a nitrogen atom having a partial structure represented by either one of the following formulae.

Preferred examples of the partial structure of the proton acceptor functional group include a crown ether structure, an aza-crown her structure, a tertiary amine structure, a secondary amine structure, a primary amine structure, a pyridine structure, an imidazole structure, a pyrazine structure and an aniline structure. The carbon number thereof is preferably from 4 to 30. Examples of the group containing such a structure include an alkyl groups a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group. The alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group are the same as those described above.

These groups each may further have a substituent.

Examples of the substituent which the above-described groups each may further have include a halogen atom, a hydroxyl group, a nitro groups a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having a carbon number of 3 to 10), an aryl group (preferably having a carbon number of 6 to 14), an alkoxy group (preferably having a carbon number of 1 to 10); an acyl group (preferably having a carbon number of 2 to 20), an acyloxy group (preferably having a carbon number of 2 to 10), an alkoxycarbonyl group (preferably having a carbon number of 2 to 20), and an aminoacyl group (preferably having a carbon number of 2 to 20). As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 20). As for the aminoacyl group, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 20).

The proton acceptor functional group may be substituted by an organic group having a bond which is breakable by an acid. Examples of the organic group having a bond breakable by an acid include an amido groups an ester group (preferably a tertiary alkyloxycarbonyl group), an acetal group (preferably a 1-alkyloxy-alkyloxy group), a carbamoyl group and a carbonate group.

When Q₁ and Q₂ are combined with each other to form a ring and the ring formed has a proton acceptor functional group, examples of the structure therefor include a structure where the organic group of Q₁ or Q₂ is flier bonded by an alkylene group, an oxy group, an imino group or the like.

In formula (A-I), at least either one of X₁ and X₂ is preferably —SO₂—.

The compound having a structure represented by formula (A-I) preferably has a structure represented by the following formula (A-II): Q₁-X₁—NH—X₂-A-(X₃)_(n)—B-Q₃  (A-II)

In formula (A-II), Q₁ and Q₃ each independently represents a monovalent organic group, provided that either one of Q₁ and Q₃ has a proton acceptor functional group. Q₁ and Q₃ may be combined with each other to form a ring, and the ring formed may have a proton acceptor functional group.

X₁, X₂ and X₃ each independently represents —CO or —SO₂—.

A represents a divalent linking group.

B represents a single bond, an oxygen atom or —N(Q_(x))-.

Q_(x) represents a hydrogen atom or a monovalent organic group.

When B is —N(Q_(x))-, Q₃ and Q_(x) may be combined with each other to form a ring.

n represents 0 or 1.

Q₁ has the same meaning as Qt in formula (A-I).

Examples of the organic group of Q₃ are the same as those of the organic group of Q₁ and Q₂ in formula (A-I).

The divalent linking group of A is preferably a divalent linking group having a carbon number of 1 to 8 and containing a fluorine atom, and examples thereof include a fluorine atom-containing alkylene group having a carbon number of 1 to 8, preferably from 2 to 6, more preferably from 2 to 4, and a fluorine atom-containing phenylene group, with a fluorine atom-containing alkylene group being preferred. The alkylene chain may contain a linking group such as oxygen atom and sulfur atom. The alkylene group is preferably an alkylene group where from 30 to 100% by number of the hydrogen atom is replaced by a fluorine atom, more preferably a perfluoroalkylene group, still more preferably a perfluoroethylene group, a perfluoropropylene group or a perfluorobutylene group.

The monovalent organic group of Q_(x) is preferably an organic group having a carbon number of 4 to 30, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group. Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group are the same as those described above for Q₁ and Q₂.

In formula (A-II), X₁, X₂ and X₃ each is preferably —SO₂—.

Specific examples of the compound represented by formula (A-I) are set forth below, but the present invention is not limited thereto.

The compound capable of generating a compound represented by formula (A-I) upon irradiation with actinic rays or radiation is preferably a sulfonium salt compound of the compound represented by formula (A-I), or an iodonium salt compound of the compound represented by formula (A-I).

The compound capable of generating a compound represented by formula (A-I) upon irradiation with actinic rays or radiation is more preferably a compound represented by the following formula (A1) or (A2):

In formula (A1), R₂₀₁, R₂₀₂ and R₂₀₃ each independently represents an organic group.

X⁻ represents an anion of the compound represented by formula (A-I). In the anion of the compound represented by formula (A-I), the nitrogen atom shown in formula (A-I) becomes a negative ion.

The carbon number of the organic group of R₂₀₁, R₂₀₂ and R₂₀₃ is generally from 1 to 30, preferably from 1 to 20.

Two members out of R₂₀₁ to R₂₀₃ may be combined to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amido bond or a carbonyl group. Examples of the group formed resulting from two members out of R₂₀₁ to R₂₀₃ are combined include an alkylene group (e.g., butylene, pentylene).

Specific examples of the organic group of R₂₀₁, R₂₀₂ and R₂₀₃ include the corresponding groups in the compounds (A1a), (A1b) and (A1c) described later.

The compound may be a compound having a plurality of structures represented by formula (A1). For example, the compound may be a compound having a structure that least one of R₂₀₁ to R₂₀₃ in the compound represented by formula (A1) is bonded to at least one of R₂₀₁ to R₂₀₃ in another compound represented by formula (A1).

The component (A1) is more preferably a compound (A1a), (A1b) or (A1c) described below.

The compound (A1a) is an arylsulfonium compound where at least one of R₂₀₁ to R₂₀₃ in formula (A1) is an aryl groups that is, a compound having arylsulfonium as the cation.

In the arylsulfonium compound, R₂₀₁ to R₂₀₃ all may be an aryl group or a part of R₂₀₁ to R₂₀₃ may be an aryl group with the remaining being an alkyl group or a cycloalkyl group.

Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, a diarylcycloalkylsulfonium compound, an aryldialkylsulfonium compound, a aryldicycloalkylsulfonium compound and an arylalkylcycloalkylsulfonium compound.

The aryl group in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by the removal of one hydrogen atom from a pyrrole), a furan residue (a group formed by the removal of one hydrogen atom from a furan), a thiophene residue (a group formed by the removal of one hydrogen atom from a thiophene), an indole residue (a group formed by the removal of one hydrogen atom from an indole), a benzofuran residue (a group formed by the removal of one hydrogen atom from a benzofuran) and a benzothiophene residue (a group formed by the removal of one hydrogen atom from a benzothiophene). In the case where the arylsulfonium compound has two or more aryl groups, these two or more aryl groups may be the same of different.

The alkyl group which is present, if desired, in the arylsulfonium compound is preferably a linear or branched alkyl group having a carbon number of 1 to 15, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a tert-butyl group.

The cycloalkyl group which is present, if desired, in the arylsulfonium compound is preferably a cycloalkyl group having a carbon number of 3 to 15, and examples thereof include a cyclopropyl group, a cyclobutyl group and a cyclohexyl group.

The aryl group, alkyl group and cycloalkyl group of R₂₀₁ to R₂₀₃ each may have, as the substituent, an alkyl group (for example, an alkyl group having a carbon number of 1 to 15), a cycloalkyl group (for example, a cycloalkyl group having a carbon number of 3 to 15), an aryl group (for example, an aryl group having a carbon number of 6 to 14), an alkoxy group (for example, an alkoxy group having a carbon number of 1 to 15), a halogen atom, a hydroxy group or a phenylthio group. The substituent is preferably a linear or branched alkyl group having a carbon number of 1 to 12, a cycloalkyl group having a carbon number of 3 to 12, or a linear, branched or cyclic alkoxy group having a carbon number of 1 to 12, and most preferably an alkyl group having a carbon number of 1 to 4, or an alkoxy group having a carbon number of 1 to 4. The substituent may be substituted to any one of three members R₂₀₁ to R₂₀₃ or may be substituted to a of these three members. In the case where R₂₀₁ to R₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group,

The compound (A1b) is described below.

The compound (A1b) is a compound when R₂₀₁ to R₂₀₃ in formula (A1) each independently represents an organic group having no aromatic ring. The aromatic ring as used herein includes an aromatic ring having a heteroatom.

The aromatic ring-free organic group of R₂₀₁ to R₂₀₃ has a carbon number of generally from 1 to 30, preferably from 1 to 20.

R₂₀₁ to R₂₀₃ each independently represents preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocyloalkyl group or an alkoxycarbonylmethyl group, still more preferably a linear or branched 2-oxoalkyl group. The alkyl group of R₂₀₁ to R₂₀₃ may be either linear or branched and, is preferably a linear or branched alkyl group having a carbon number of 1 to 20 (e.g., methyl, ethyl, propyl, butyl, pentyl). The alkyl group of R₂₀₁ to R₂₀₃ is more preferably a linear or branched 2-oxoalkyl group or an alkoxycarbonylmethyl group.

The cycloalkyl group of R₂₀₁ to R₂₀₃ is preferably a cycloalkyl group having a carbon number of 3 to 10 (e.g., cyclopentyl, cyclohexyl, norbornyl). The cycloalkyl group of R₂₀₁ to R₂₀₃ is more preferably a 2-oxocycloalkyl group.

The linear or branched 2-oxoalkyl group of R₂₀₁ to R₂₀₃ may have a double bond in the chain and is preferably a group having >C═O at the 2-position of the alkyl group above.

The 2-oxocycloalkyl group of R₂₀₁ to R₂₀₃ may have a double bond in the chain and is preferably a group having >C═O at the 2-position of the cycloalkyl group above.

The alkoxy group in the alkoxycarbonylmethyl group of R₂₀₁ to R₂₀₃ is preferably an alkoxy group having a carbon number of 1 to 5 (e.g., methoxy, ethoxy, propoxy, butoxy, pentoxy).

R₂₀₁ to R₂₀₃ each may be further substituted by a halogen atom, an alkoxy group (for example, an alkoxy group having a carbon number of 1 to 5), an alkoxycarbonyl group (for example, an alkoxycarbonyl group having a carbon number of 1 to 5), a hydroxyl group, a cyano group or a nitro group.

The compound (A1c) is a compound represented by the following formula (A1c), and this is a compound having an arylacylsulfonium salt structure.

In formula (A1c), R₂₁₃ represents an aryl group which may have a substituent, and is preferably a phenyl group or a naphthyl group.

Preferred examples of the substituent on R₂₁₃ include an alkyl group, an alkoxy group, an acyl group, a nitro group, a hydroxyl group, an alkoxycarbonyl group and a carboxy group.

R₂₁₄ and R₂₁₅ is each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.

Y₂₀₁ and Y₂₀₂ each independently represents an alkyl group, a cycloalkyl group, an aryl group or a vinyl group.

X⁻ represents an anion of the compound represented by formula (A-I).

R₂₁₃ and R₂₁₄ may be combined with each other to for a ring structure, R₂₁₄ and R₂₁₅ may be combined with each other to form a ring structure, and Y₂₀₁ and Y₂₀₂ may be combined with each other to form a ring structure. The ring structure formed may contain an oxygen atom, a sulfur atom, an ester bond or an amide bond. Examples of the group formed resulting from each pair of R₂₁₃ and R₂₁₄, R₂₁₄ and R₂₁₅ or Y₂₀₁ and Y₂₀₂ being combined include a butylene group and a pentylene group.

The alkyl group of R₂₁₄, R₂₁₅, Y₂₀₁ and Y₂₀₂ is preferably a linear or branched alkyl group having a carbon number of 1 to 20. The alkyl group of Y₂₀₁ and Y₂₀₂ is more preferably a 2-oxoalkyl group having >C═O at the 2-position of the alkyl group, an alkoxycarbonylalkyl group (preferably with an alkoxy group having a carbon number of 2 to 20), or a carboxyalkyl group.

The cycloalkyl group of R₂₁₄, R₂₁₅, Y₂₀₁ and Y₂₀₂ is preferably a cycloalkyl group having a carbon number of 3 to 20.

The aryl group of Y₂₀₁ and Y₂₀₂ is preferably a phenyl group or a naphthyl group.

Y₂₀₁ and Y₂₀₂ each is preferably an alkyl group having a carbon number of 4 or more, more preferably from 4 to 6, still more preferably from 4 to 12.

At least either one of R₂₁₄ and R₂₁₅ is preferably an alkyl group, and more preferably, R₂₁₄ and R₂₁₅ both are an alkyl group.

In formula (A2), R₂₀₄ and R₂₀₅ each independently represents an aryl group, an alkyl group or a cycloalkyl group.

X⁻ represents an anion of the compound represented by formula (A-I).

The aryl group of R₂₀₄ and R₂₀₅ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group of R₂₀₄ and R₂₀₅ may be an aryl group having a heterocyclic suture containing an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by the removal of one hydrogen atom from a pyrrole), a furan residue (a group formed by the removal of one hydrogen atom from a a thiophene residue (a group formed by the removal of one hydrogen atom from a thiophene), an indole residue (a group formed by the removal of one hydrogen atom from an indole), a benzofuran residue (a group formed by the removal of one hydrogen atom from a benzofuran) and a benzothiophene residue (a group formed by the removal of one hydrogen atom from a benzothiophene).

The alkyl group of R₂₀₄ and R₂₀₅ may be either linear or branched and is preferably a linear or branched alkyl group having a carbon number of 1 to 10 (e.g., methyl, ethyl, propyl, butyl, pentyl).

The cycloalkyl group of R₂₀₄ and R₂₀₅ is preferably a cycloalkyl group having a carbon number of 3 to 10 (e.g., cyclopentyl, cyclohexyl, norbornyl).

R₂₀₄ and R₂₀₅ each may have a substituent, and examples of the substituent which R₂₀₄ and R₂₀₅ each may have include an alkyl group (for example, an alkyl group having a carbon number of 1 to 15), a cycloalkyl group (for example a cycloalkyl group having a carbon number of 3 to 15), an aryl group (for example, an aryl group having a carbon number of 6 to 15), an alkoxy group (for example, an alkoxy group having a carbon number of 1 to 15), a halogen atom, a hydroxyl group and a phenylthio group.

The compound (A) is preferably a compound represented by formula (A1), more preferably a compound represented by any one of formulae (A1a) to (A1c).

Specific examples of the compound (A) are set fort below, but the present invention is not limited thereto.

One species of the compound (A) may be used alone or two or more species thereof may be used in combination.

The content of the compound (A) in the positive resist composition of the present invention is preferably from 0.1 to 20 mass %, more preferably from 0.1 to 10 mass %, based on the solid content of the composition.

The compound (A) can be easily synthesized by using a general sulfonic acid esterification reaction or sulfonamidation reaction. For example, this compound may be obtained by a method of selectively reacting one sulfonyl halide moiety of a bis-sulfonyl halide compound with an amine, alcohol or the like containing a partial structure represented by formula (A-I) to form a sulfonamide bond or a sulfonic acid ester bond, and then hydrolyzing the other sulfonyl halide moiety or a method of ring-opening a cyclic sulfonic anhydride with an amine or alcohol containing a partial structure represented by formula (A-I). The amine or alcohol containing a partial structure represented by formula (A-I) can be synthesized by reacting an amine or alcohol with an anhydride (e.g., (R′O₂C)₂O, R′O₂OCl) or an acid chloride compound under the basic condition.

[3] (Z) Compound Capable of Generating an Acid Upon Irradiation with Actinic Rays or Radiation

The positive resist composition of the present invention preferably comprises a compound capable of generating an acid upon irradiation with actinic rays or radiation (hereinafter sometimes referred to as an “acid generator”). The acid generator which can be used may be appropriately selected from a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photo-decoloring agent for coloring matters, a photo-discoloring agent, a known compound capable of generating an acid upon irradiation with actinic rays or radiation, which is used for microresist and the like, and a mixture thereof.

Examples thereof include diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, imidosulfonate, oxime sulfonate, diazodisulfone disulfone and o-nitrobenzyl sulfonate.

Also, a compound where the above-described group or compound capable of generating an acid upon irradiation with actinic rays or radiation is introduced into the polymer main or side chain, such as compounds described in U.S. Pat. No. 3,849,137, German Patent 3,914,407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853 and JP-A-63-146029, may be used.

Furthermore, a compound capable of generating an acid by the effect of light described, for example, in U.S. Pat. No. 3,779,778 and European Patent 126,712 may also be used.

Among the compounds capable of generating an acid upon irradiation with actinic rays or radiation, preferred are the compounds represented by the following formulae (ZI), (ZII) and (ZIII):

In formula (ZI), R₂₀₁, R₂₀₂ and R₂₀₃ each independently represents an organic group.

The number of carbons in the organic group as R₂₀₁, R₂₀₃ is generally from 1 to 30, preferably from 1 to 20.

Two members out of R₂₀₁ to R₂₀₃ may be combined to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group. Examples of the group formed resulting from two members out of R₂₀₁ to R₂₀₃ being combined include an alkylene group (e.g. butylene, pentylene),

Z′ represents a non-nucleophilic anion.

Examples of the non-nucleophilic anion of Z′ include sulfonate anion, carboxylate anion, sulfonylimide anion, bis(alkylsulfonyl)imide anion and tris(alkylsulfonyl)methyl anion.

The non-nucleophilic anion is an anion having an extremely low ability of causing a nucleophilic reaction and this anion can suppress the decomposition in aging due to intramolecular nucleophilic reaction. By is anion, the aging stability of the resist is enhanced.

Examples of the sulfonate anion include aliphatic sulfonate anion, aromatic sulfonate anion and camphorsulfonate anion.

Examples of the carboxylate anion include aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion.

The aliphatic moiety in the aliphatic sulfonate anion may be an alkyl group or a cycloalkyl group but is preferably an alkyl group having a carbon number of 1 to 30 or a cycloalkyl group having a carbon number of 3 to 30, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group and a boronyl group.

The aromatic group in the aromatic sulfonate anion is preferably a aryl group having a carbon number of 6 to 14, and examples thereof include a phenyl group, a tolyl group and a naphthyl group.

The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion each may have a substituent. Examples of the substituent for the alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion include a nitro group, a halogen atom (e.g., fluorine, chlorine, bromine, iodine), a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 5), a cycloalkyl group preferably having a carbon number of 3 to 15), an aryl group preferably having a carbon number of 6 to 14), an alkoxycarbonyl group (preferably having a carbon number of 2 to 7), an acyl group (preferably having a carbon number of 2 to 12) and an alkoxycarbonyloxy group (preferably having a carbon number of 2 to 7). As for the aryl group or ring structure in each group, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15).

Examples of the aliphatic moiety in the aliphatic carboxylate anion include the same alkyl group and cycloalkyl group as in the aliphatic sulfonate anion.

Examples of the aromatic group in the aromatic carboxylate anion include the same aryl group as in the aromatic sulfonate anion.

The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having a carbon number of 6 to 12, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and a naphthylmethyl group.

The alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion each may have a substituent. Examples of the substituent for the alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion include the same halogen atom, alkyl group, cycloalkyl group, alkoxy group and alkylthio group as in the aromatic sulfonate anion.

Examples of the sulfonylimide anion include saccharin anion.

The alkyl group in the bis(alkylsulfonyl)imide anion and tris(alkylsulfonyl)methyl anion is preferably an alkyl group having a carbon number of 1 to 5, and examples thereof include a methyl group, an ethyl groups a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a pentyl group and a neopentyl group. Examples of the substituent for such an alkyl group include a halogen atom, a halogen atom-substituted alkyl group, an alkoxy group and an alkylthio group, with a fluorine atom-substituted alkyl group being preferred.

Other examples of the non-nucleophilic anion include fluorinated phosphorus, fluorinated boron and fluorinated antimony.

The non-nucleophilic anion of Z⁻ is preferably an aliphatic sulfonate anion with the α-position of sulfonic acid being substituted by a fluorine atom, an aromatic sulfonate anion substituted by a fluorine atom or a group having a fluorine atom, a bis(alkylsulfonyl)imide anion with the alkyl group being substituted by a fluorine atom, or a tris(alkysulfonyl)methide anion with the alkyl group being substituted by a fluorine atom, more preferably a perfluoroaliphatic sulfonate anion having a carbon number of 4 to 8 or a benzenesulfonate anion having a fluorine atom, still more preferably nonafluorobutanesulfonate anion, perfluorooctanesulfonate anion, pentafluorobenzenesulfonate anion or 3,5-bis(trifluoromethyl)benzenesulfonate anion.

Examples of the organic group of R₂₀₁, R₂₀₂ and R₂₀₃ include corresponding groups in the compounds (ZI-1), (ZI-2) and (ZI-3) which are described later.

The compound may be a compound having a plurality of structures represented by formula (ZI), for example, may be a compound having a structure that at least one of R₂₀₁ to R₂₀₃ in the compound represented by formula (ZI) is bonded to at least one of R₂₀₁ to R₂₀₃ in another compound represented by formula (ZI).

The component (ZI) is more preferably a compound (ZI-1), (ZI-2) or (ZI-3) described below.

The compound (ZI-1) is an arylsulfonium compound where at least one of R₂₀₁ to R₂₀₃ in formula (ZI) is an aryl group, that is, a compound having an arylsulfonium as the cation.

In the arylsulfonium compound, R₂₀₁ to R₂₀₃ all may be an aryl group or a part of R₂₀₁ to R₂₀₃ may be an aryl group with the remaining being an alkyl group or a cycloalkyl group.

Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound an aryldialkylsulfonium compound, a diarylcycloalkylsulfonium compound and an aryldicycloalkylsulfonium compound.

The aryl group in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by the removal of one hydrogen atom from a pyrrole), a furan residue (a group formed by the removal of one hydrogen atom from a furan), a thiophene residue (a group formed by the removal of one hydrogen atom from a thiophene), an indole residue (a group formed by the removal of one hydrogen atom from an indole), a benzofuran residue (a group formed by the removal of one hydrogen atom from a benzofuran) and a benzothiophene residue (a group formed by the removal of one hydrogen atom from a benzothiophene). In the case where the arylsulfonium compound has two or more aryl groups, these two or more aryl groups may be the same of different.

The alkyl group or cycloalkyl group which is present, if desired, in the arylsulfonium compound is preferably a linear or branched alkyl group having a carbon number of 1 to 15 or a cycloalkyl group having a carbon number of 3 to 15, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclopropyl group, a cyclobutyl group and a cyclohexyl group.

The aryl group, alkyl group and cycloalkyl group of R₂₀₁ to R₂₀₃ each may have, as the substituent, an alkyl group (for example, an alkyl group having a carbon number of 1 to 15), a cycloalkyl group (for example, a cycloalkyl group having a carbon number of 3 to 15), an aryl group (for example, an aryl group having a carbon number of 6 to 14), an alkoxy group (for example, an alkoxy group having a carbon number of 1 to 15), a halogen atom, a hydroxyl group or a phenylthio group. The substituent is preferably a linear or branched alkyl group having a carbon number of 1 to 12, a cycloalkyl group having a carbon number of 3 to 12, or a linear, branched or cyclic alkoxy group having a carbon number of 1 to 12, more preferably an alkyl group having a carbon number of 1 to 4, or an alkoxy group leaving a carbon number of 1 to 4. The substituent may be substituted to any one of three members R₂₀₁ to R₂₀₃ or may be substituted to all of these three members. In the case where R₂₀₁ to R₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

The compound (ZI-2) is described below.

The compound (ZI-2) is a compound where R₂₀₁ to R₂₀₃ in formula (ZI) each independently represents an organic group having no aromatic ring. The aromatic ring as used herein includes an aromatic ring containing a heteroatom.

The aromatic ring-free organic group of R₂₀₁ to R₂₀₃ has a carbon number of generally 1 to 30, preferably from 1 to 20.

R₂₀₁ to R₂₀₃ each independently represents preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or an alkoxycarbonylmethyl group, still more preferably a linear or branched 2-oxoalkyl group.

The alkyl group or cycloalkyl group of R₂₀₁ to R₂₀₃ is preferably a linear or branched alkyl group having a carbon number of 1 to 10 (e.g., methyl, ethyl, propyl, butyl, pentyl) or a cycloalkyl group having a carbon number of 3 to 10 (e.g., cyclopentyl, cyclohexyl, norbornyl). The alkyl group is more preferably a 2-oxoalkyl group or an alkoxycarbonylmethyl group. The cycloalkyl group is more preferably a 2-oxocycloalkyl group.

The 2-oxoalkyl group may be either linear or branched and is preferably a group having >C═O at the 2-position of the alkyl group above.

The 2-oxocycloalkyl group is preferably a group having >C═O at the 2-position of the cycloalkyl group above.

The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having a carbon number of 1 to 5 (e.g., methoxy, ethoxy, propoxy, butoxy, pentoxy).

R₂₀₁ to R₂₀₃ each may be further substituted by a halogen atom, an alkoxy group (for example, an alkoxy group having a carbon number of 1 to 5), a hydroxyl group, a cyano group or a nitro group.

The compound (ZI-3) is a compound represented by the following formula (ZI-3), and this is a compound having a phenacylsulfonium salt structure.

In formula (ZI-3), R_(1c) to R_(5c) each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom.

R_(6c) and R_(7c) each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.

R_(x) and R_(y) each independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.

Any two or more members out of R_(1c) to R_(5c), the pair of R_(6c) and R_(7c), or the pair of R_(x) and R_(y) may be combined with each other to form a ring structure, and the ring structure may contain an oxygen atom, a sulfur atom, an ester bond or an amido bond. Examples of the group formed resulting from any two or more members out of R_(1c) to R_(5c), the pair of R_(6c) and R_(7c) or the pair of R_(x) and R_(y) being combined include a butylene group and a pentylene group.

Zc⁻ represents a non-nucleophilic anion, and examples thereof are the same as those of the non-nucleophilic anion of Z′ in formula (ZI).

The alkyl group of R_(1c) to R_(7c) may be either linear or branched and is, for example, an alkyl group having a carbon number of 1 to 20, preferably a linear or branched alkyl group having a carbon number of 1 to 12 (e.g., methyl, ethyl, linear or branched propyl, linear or branched butyl, linear or branched pentyl). The cycloalkyl group is, for example, a cycloalkyl group having a carbon number of 3 to 8 (e.g., cyclopentyl, cyclohexyl).

The alkoxy group of R_(1c) to R_(5c) may be linear, branched or cyclic and is, for example, an alkoxy group having a carbon number of 1 to 10, preferably a linear or branched alkoxy group having a carbon number of 1 to 5 (e.g., methoxy, ethoxy, linear or branched propoxy, linear or branched butoxy, linear or branched pentoxy) or a cyclic alkoxy group having a carbon number of 3 to 8 (e.g., cyclopentyloxy, cyclohexyloxy).

A compound where any one of R_(1c) to R_(5c) is a linear or branched alkyl group, a cycloalkyl group or a linear, branched or cyclic alkoxy group is preferred, and a compound where the sum of carbon numbers of R_(1c) to R_(5c) is from 2 to 15 is more preferred. In is case, the solubility in a solvent is more enhanced and generation of particles during storage can be suppressed.

Examples of the alkyl group and cycloalkyl group of R^(x) and R_(y) include the same alkyl group and cycloalkyl group as in R_(1c) to R_(7c). Among these, a 2-oxoalkyl group, a 2-oxocycloalkyl group and an alkoxycarbonylmethyl group are preferred.

Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include a group having >C═O at the 2-position of the alkyl group or cycloalkyl group of R_(1c) to R_(7c).

Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy group as in R_(1c) to R_(5c).

R_(x) and R_(y) each is preferably an alkyl or cycloalkyl group having a carbon number of 4 or more, more preferably 6 or more, still more preferably 8 or more.

In formulae (ZII) and (ZIII), R₂₀₄ to R₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.

The aryl group of R₂₀₄ to R₂₀₇ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group of R₂₀₄ and R₂₀₇ may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by the removal of one hydrogen atom from a pyrrole), a furan residue (a group formed by the removal of one hydrogen atom from a furan), a thiophene residue (a group formed by the removal of one hydrogen atom from a thiophene), an indole residue (a group formed by the removal of one hydrogen atom from an indole), a benzofuran residue (a group formed by the removal of one hydrogen atom from a benzofuran) and a benzothiophene residue (a group formed by the removal of one hydrogen atom from a benzothiophene).

The alkyl group or cycloalkyl group of R₂₀₄ to R₂₀₇ is preferably a linear or branched alkyl group having a carbon number of 1 to 10 (e.g., methyl, ethyl, propyl, butyl, pentyl) or a cycloalkyl group having a carbon number of 3 to 10 (e.g., cyclopentyl, cyclohexyl, norbornyl).

The aryl group, alkyl group and cycloalkyl group of R₂₀₄ to R₂₀₇ each may have a substituent. Examples of the substituent which the aryl group, alkyl group and cycloalkyl group of R₂₀₄ to R₂₀₇ each may have include an alkyl group (for example, an alkyl group having a carbon number of 1 to 15), a cycloalkyl group (for example, a cycloalkyl group having a carbon number of 3 to 15), an aryl group (for example, an aryl group having a carbon number of 6 to 15), an alkoxy group (for example, an alkoxy group having a carbon number of 1 to 15), a halogen atom, a hydroxyl group and a phenylthio group.

Z′ represents a non-nucleophilic anion, and examples thereof are the same as those of the non-nucleophilic anion of Z′ in formula (ZI).

Other examples of the compound capable of generating an acid upon irradiation with actinic rays or radiation, which can be used, include the compounds represented by the following formulae (ZIV), (ZV) and (ZVI):

In formulae (ZIV) to (ZVI), Ar₃ and Ar₄ each independently represents an aryl group.

R₂₀₆, R₂₀₇ and R₂₀₈ each independently represents an alkyl group, a cycloalkyl group or an aryl group.

A represents an alkylene group, an alkenylene group or an arylene group.

Among the compounds capable of generating an acid upon irradiation with actinic rays or radiation, more preferred are the compounds represented by formulae (ZI) to (ZIII).

Also, the compound capable of generating an acid upon irradiation with actinic rays or radiation is preferably a compound capable of generating an acid having one sulfonic acid group or imide group, more preferably a compound capable of generating a monovalent perfluoroalkanesulfonic acid, a compound capable of generating a monovalent aromatic sulfonic acid substituted by a fluorine atom or a fluorine atom-containing group, or a compound capable of generating a monovalent imide acid substituted by a fluorine atom or a fluorine atom-containing group. In particular, the usable acid generator preferably generates a fluoro-substituted alkanesulfonic acid, a fluoro-substituted benzenesulfonic acid or a fluoro-substituted imide acid, which are an acid having a pKa of −1 or less, and in this case, the sensitivity can be enhanced.

Among the compounds capable of generating an acid upon irradiation with actinic rays or radiation, particularly preferred compounds (z1) to (z66) are set forth below.

One kind of an acid generator may be used alone or two or more kinds of acid generators may be used in combination.

The content of the acid generator in the positive resist composition is preferably from 0.1 to 20 mass %, more preferably from 0.5 to 10 mass %, still more preferably from 1 to 7 mass %, based on the entire solid content of the positive resist composition.

<Other Components>

[4] (G) Nitrogen-Containing Basic Compound

In the present invention, (G) a nitrogen-containing basic compound is preferably used from the standpoint of enhancing the performance such as resolution or the storage stability.

Preferred structures of the nitrogen-containing basic compound include structures represented by the following formulae (A) to (E).

In these formulae, R²⁵⁰, R²⁵¹ and R²⁵² each independently represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably having a carbon number of 3 to 20), or an aryl group (preferably having a carbon number of 6 to 20), and R²⁵⁰ and R²⁵¹ may be combined with each other to from a ring. These groups each may have a substituent. The alkyl or cycloalkyl group having a substituent is preferably an aminoalkyl group having a carbon number of 1 to 20, an aminocycloalkyl group having a carbon number of 3 to 20, a hydroxyalkyl group having a carbon number of 1 to 20, or a hydroxycycloalkyl group having a carbon number of 3 to 20.

The alkyl chain thereof may contain an oxygen atom, a sulfur atom or a nitrogen atom.

R²⁵³, R²⁵⁴, R²⁵⁵ and R²⁵⁶ each independently represents an alkyl group having a carbon number of 1 to 6 or a cycloalkyl group having a carbon number of 3 to 6.

Preferred examples of the compound include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine and piperidine, and those compounds each may have a substituent. More preferred examples of the compound include a compound having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, a onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and/or an ether bond; and an aniline derivative having a hydroxyl group and/or an ether bond.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole and benzimidazole. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of the compound having an onium hydroxide structure include a triarylsulfonium hydroxide, a phenacylsulfonium hydroxide and a sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris(tert-butylphenyl)sulfonium hydroxide, bis(tert-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide and 2-oxopropylthiophenium hydroxide. The compound having an onium carboxylate structure is a compound where the anion moiety of the compound having an onium hydroxide structure is converted into a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate and perfluoroalkyl carboxylate. Examples of the compound having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of the amine compound include 2,6-diisopropylaniline and N,N-dimethylaniline. Examples of the alkylamine derivative having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine and tris(methoxyethoxyethyl)amine, Examples of the aniline derivative having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline.

One of these basic compounds may be used alone, or two or more species thereof may be used in combination. However, when the amount of the component (B) used is 0.05 mass % or more, the basic substance may or may not be used. In the case of using the basic compound, the amount used thereof is usually from 0.001 to 10 mass %, preferably from 0.01 to 5 mass %, based on the solid content of the resist composition. The amount used is preferably 0.001 mass % or more for obtaining a sufficiently high addition effect and preferably 10 mass % or less in view of sensitivity and developability of unexposed area.

[5] (H) Fluorine- and/or Silicon-Containing Surfactant

The resist composition of the present invention preferably further contains any one of fluorine- and/or silicon-containing surfactants (a fluorine-containing surfactant, a silicon-containing surfactant or a surfactant containing both a fluorine atom and a silicon atom), or two or more thereof.

When the resist composition of the present invention contains a fluorine- and/or silicon-containing surfactant, a resist pattern with good sensitivity, resolution and adhesion and less development defect can be obtained at the time of using an exposure light source of 250 nm or less, particularly 220 nm or less.

Examples of the fluorine- and/or silicon-containing surfactant include surfactants described in JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A-2002-277862 and U.S. Pat. Nos. 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511 and 5,824,451. The following commercially available surfactants each may also be used as it is.

Examples of the commercially available surfactant which can be used include a fluorine-containing surfactant and a silicon-containing surfactant, such as EFtop EF301 and EF303 (produced by Shin-Akita Kasei K.K.), Florad FC430 and 431 (produced by Sumitomo 3M Inc.), Megafac F171, F173, F176, F189 and R08 (produced by Dainippon Ink & Chemicals, Inc), Suflon S-382, SC101, 102, 103, 104, 105 and 106 (produced by Asahi Glass Co., Ltd.), and Troysol S-366 produced by Troy Chemical). In addition, a polysiloxane polymer KP-341 (produced by Shin-Etsu Chemical Co., Ltd.) may also be used as the silicon-containing surfactant.

Other than these known surfactants, a surfactant using a polymer having a fluoro-aliphatic group which is derived from a fluoro-aliphatic compound produced by a telomerization process (also called a telomer process) or an oligomerization process (also called an oligomer process), may be used. The fluoro-aliphatic compound can be synthesized by the method described in JP-A-2002-90991.

The polymer having a fluoro-aliphatic group is preferably a copolymer of a fluoro-aliphatic group-containing monomer with a poly(oxyalkylene)) acrylate and/or a (poly(oxyalkylene)) methacrylate, and the polymer may have an irregular distribution or may be a block copolymer, Examples of the poly(oxyalkylene) group include a poly(oxyethylene) group, a poly(oxypropylene) group and a poly(oxybutylene group). The poly(oxyalkylene) group may also be a unit having alkylenes differing in the chain length within the some chain, such as block-inked poly(oxyethylene, oxypropylene and oxyethylene) and block-linked poly(oxyethylene and oxypropylene). The copolymer of a fluoro-aliphatic group-containing monomer with a poly(oxyalkylene)) acrylate (or methacrylate) may be not only a binary copolymer but also a ternary or greater copolymer obtained by simultaneously copolymerizing two or more different fluoro-aliphatic group-containing monomers or two or more different (poly(oxyalkylene)) acrylates (or methacrylates).

Examples thereof include commercially available surfactants such as Megafac F178, F470, F-473, F-475, F-476 and F472 (produced by Dainippon Ink & Chemicals, Inc.), and ter include a copolymer of a C₆F₁₃ group-containing acrylate (or methacrylate) with a (poly(oxyalkylene)) acrylate (or methacrylate), a copolymer of a C₆F₁₃ group-containing acrylate (or methacrylate) with (poly(oxyethylene)) acrylate (or methacrylate) and poly(oxypropylene)) acrylate (or methacrylate), a copolymer of a C₈F₁₇ group-containing acrylate (or methacrylate) with a (poly(oxyalkylene)) acrylate (or methacrylate), and a copolymer of a C₈F₁₇ group-containing acrylate (or methacrylate) with poly(oxyethylene)) acrylate (or methacrylate) and (Poly(oxypropylene)) acrylate (or methacrylate).

The amount of the fluorine- and/or silicon-containing surfactant used is preferably from 0.0001 to 2 mass %, more preferably from 0.001 to 1 mass %, based on the entire amount of the resist composition (excluding the solvent).

[6] Organic Solvent

The resist composition of the present invention is used by dissolving the above-described components in a predetermined organic solvent.

Examples of the organic solvent which can be used include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ethers 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N,N-dimethylformamide, dimethylsulfoxide, N-methylpyrolidone and tetrahydrofuran.

The solvent for use in the present invention is preferably a solvent having at least one ketone structure.

The solvent having a ketone structure includes a chain ketone solvent and a cyclic ketone solvent A compound having a total carbon number of 5 to 8 is preferred in view of good coatability.

Examples of the chain ketone solvent include 2-heptanone, methyl ethyl ketone and methyl isobutyl ketone, with 2-heptanone being preferred.

Examples of the cyclic ketone solvent include cyclopentanone, 3-methyl-2-cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, cycloheptanone, cyclooctanone and isophorone, with cyclohexanone and cycloheptanone being preferred.

The solvent is preferably used as a sole solvent having a ketone structure or as a mixed solvent with another solvent. Examples of the solvent mixed (solvent used in combination) include a propylene glycol monoalkyl ether carboxylate, an alkyl lactate, a propylene glycol monoalkyl ether, an alkyl alkoxypropionate and a lactone compound.

Examples of the propylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl other acetate, propylene glycol monomethyl ether propionate and propylene glycol monoethyl ether acetate.

Examples of the alkyl lactate include methyl lactate and ethyl lactate.

Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether and propylene glycol monoethyl ether.

Examples of the alkyl alkoxypropionate include methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate and ethyl ethoxypropionate.

Examples of the lactone compound include γ-butyrolactone.

The solvent used in combination is preferably a propylene glycol monoalkyl ether carboxylate, an alkyl lactate or a propylene glycol monoalkyl ether, more preferably propylene glycol monomethyl ether acetate.

By virtue of mixing the ketone-based solvent and the solvent used in combination, adhesion to substrate, developability, DOF and the like are improved.

The ratio (by mass) of the ketone-based solvent and the solvent used in combination is preferably from 10/90 to 95/5, more preferably from 20/80 to 80/20, still more preferably from 30/70 to 70/30.

From the standpoint of enhancing uniformity of film thickness or performance against development defect, a high boiling point solvent having a boiling point of 200° C. or more, such as ethylene carbonate and propylene carbonate, may be mixed.

The amount of the high boiling point solvent added is usually from 0.1 to 15 mass %, preferably from 0.5 to 10 mass %, more preferably from 1 to 5 mass %, based on the entire solvent.

In the present invention, a resist composition having a solid content concentration of usually from 1 to 20 mss %, preferably from 1 to 10 mass %, more preferably from 1 to 8 mass %, is prepared by using a sole solvent, preferably by using two or more kinds of solvents.

[7] Other Additives

If desired, the resist composition of the present invention may further contain, for example, a dye, a plasticizer, a surfactant other than the component (H), a photosensitizer, and a compound capable of accelerating the solubility in a developer.

In the present invention, a surfactant other than (H) the fluorine- and/or silicon-containing surfactant may also be added. Specific examples thereof include a nonionic surfactant such as polyoxyethylene alkyl ethers, polyoxyethylene alkylallyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters.

One of these surfactants may be used alone, or some species thereof may be used in combination.

[8] Pattern Forming Method

The resist composition of the present invention is used by dissolving the above-described components in a predetermined organic solvent, preferably a mixed solvent described above, and coating the obtained solution on a predetermined support as follows.

For example the resist composition is coated on a substrate (e.g., silicon/silicon dioxide-coated substrate) as used in the production of a precision integrated circuit device, by an appropriate coating method such as spinner or coater, and dried to form a photosensitive film.

The formed photosensitive film is irradiated with actinic rays or radiation through a predetermined mask, preferably baked (heated), and then developed, whereby a good pattern can be obtained.

At the irradiation of actinic rays or radiation, the exposure may be performed by filling a liquid having a refractive index higher than that of air between the photosensitive film and the lens (immersion exposure). By this exposure, resolution can be elevated.

Examples of the actinic ray or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light X-ray and electron beam. Among these, preferred is far ultraviolet light at a wavelength of 250 nm or less, more preferably 220 nm or less. Specifically, a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F₂ excimer laser (157 nm), an X-ray, an electron beam and the like are used. A KrF excimer laser (248 nm), EUV (13 nm) and an electron beam are more preferred.

In the development step, an alkali developer is used as follows. The alkali developer usable for the resist composition is an alkaline aqueous solution such as inorganic alkalis (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia), primary amines (e.g., ethylamine, n-propylamine), secondary amines (e.g., diethylamine, di-n-butylamine), tertiary amines (e.g., triethylamine, methyldiethylamine), alcohol amines (e.g., dimethylehanolamine, triethanolamine), quaternary ammonium salts (e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide) and cyclic amines (e.g., pyrrole, piperidine).

In the alkali developer, alcohols and a surfactant may also be added in an appropriate amount.

The alkali concentration of the alkali developer is usually from 0.1 to 20 mass %.

The pH of the alkali developer is usually from 10.0 to 15.0.

EXAMPLES

The present invention is described in eater detail below by referring to Examples, but the present invention should not be construed as being limited thereto.

<Compound (A)>

Synthesis Example of Compound A-1

In a 1,000 ml-volume three-neck flask equipped with a 100-ml dropping funnel and a nitrogen inlet tube, 34.4 g (200 mmol) of sulfanylamide was charged and then dissolved in 200 ml of 10% NaOH, and the resulting solution was stirred under ice cooling. Subsequently, 55.3 g (200 mmol) of 1-octanesulfonyl chloride was added dropwise trough the dropping funnel over 1 hour. After the dropwise addition, the mixed solution was stirred under ice cooling for 1 hour and after removing the ice bath, further stirred at room temperature for 3 hours. The obtained reaction solution was rendered neutral by adding concentrated hydrochloric acid thereto, and the precipitated white solid matter was collected by filtration. This solid matter was then recrystallized from water/methanol to obtain 45.1 g of the following compound as a plate-like crystal.

Separately, 16.1 g (46.9 mmol) of triphenylsulfonium bromide and 12.4 g (53.5 mmol) of silver oxide were added to 150 ml of methanol, and the resulting mixture was stirred at room temperature for 2 hours. After removing the silver salt by filtration, 16.34 g (46.9 mmol) of the compound prepared above was added to the filtrate, and this solution was further stirred for 1 hour. Subsequently, the solvent was removed, 200 ml of chloroform was added to the residue, and the organic layer was washed with water. Furthermore, the solvent was removed, and the residue was dried to obtain 20.9 g of a white solid matter.

¹H-NMR (400 MHz, CD₃OD): δ 0.93 (t, 3H), 1.34-1.46 (m, 10H), 1.81 (quin, 2H), 3.24 (t, 2H), 6.78 (d, 2H), 7.66-7.78 (m, 17H),

Synthesis Example of Compound A-6

Triphenylsulfonium bromide (8.01 g (23.34 mmol)) and 5.68 g (24.51 mmol) of silver oxide were added to 100 ml of methanol, and the resulting mixture was stirred at room temperature for 2 hours. After removing the silver salt by filtration, 5.0 g (23.34 mmol) sulfacetamide as the compound above was added to the filtrate, and this solution was further stirred for 1 hour. Thereafter, the solvent was removed, and the residue was dried to obtain 10.0 g of a white solid matter.

¹H-NMR (400 MHz, CD₃OD): δ 1.84 (s, 3H), 6.63 (d, 2H), 7.63 (d, 2H), 7.78-7.87 (m, 15H).

Synthesis Example of Compound A-8

In a nitrogen stream, a mixture containing 5.0 g (15.8 mmol) of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl difluoride and 50 ml of THF was ice-cooled, and a mixed solution containing 1.66 g (16.6 mmol) of 1-methylpiperazine, 10 ml of triethylamine and 50 ml of THF was added dropwise thereto over 60 minutes. The resulting solution was stirred under ice cooling for 1 hour and further stirred at room temperature for 1 hour. Thereafter, the organic layer was washed with water, an aqueous saturated ammonium chloride solution and water in this order and then dried over sodium sulfate. After concentrating the solvent, 2.36 g (15.8 mmol) of trifluoromethanesulfonamide and 10 ml of triethylamine were added to the residue, and this mixture was transferred to a pressure-resistant glass tube and stirred at 100° C. for 20 hours in the sealed tube. Subsequently, 100 ml of chloroform was added, and the organic layer was washed with water and then dried over sodium sulfate to obtain a brown oil. This oil was then rendered neutral by adding thereto 25 ml of methanol and 60 ml of 1.5N-HCl, and the precipitated white solid matter was collected by filtration to obtain 5.65 g of the following compound.

The solid matter (4.0 g) obtained above was dissolved in a mixed solvent containing 100 ml of methanol and 40 ml of 1M-NaOH and after adding 2.61 g (7.61 mmol) of triphenylsulfonium bromide, the resulting solution was stirred at room temperature for 3 hours. Subsequently, 200 ml of chloroform was added, the organic layer was washed with water, the solvent was removed, and the residue was purified by column chromatography (SiO₂, chloroform/methanol=10/1) to obtain the objective Compound (4.56 g) as a white solid.

¹H-NMR (400 MHz, CDCl₃): δ 2.32 (s, 3H), 2.50 (m, 4H), 3.55 (m, 4H), 7.65-7.80 (m, 15H).

¹⁹F-NMR (400 MHz, CDCl₃): δ-118.5 (m, 2F), −112.3 (m, 2F), −111.1 (m, 2F), −78.6 (m: 3F).

Other compounds were synthesized in the same manner.

<Compound (B)>

The structure, weight average molecular weight and dispersity of the compound (3) used in Examples are shown below,

EXAMPLES i) Preparation of Resist Composition (Example 1)

Component B (RA-1) 1.255 g Acid generator (z17) 0.0759 g  Component A (A-38)  0.02 g Surfactant (W-4) 0.002 g

These components were dissolved in a solvent shown in Table 2 below to prepare a solution having a solid content concentration of 6.5 mass %, and this solution was filtered through a 0.1-μm polytetrafluoroethylene-made filter to obtain a resist solution. The resist solutions of other Examples and Comparative Examples were obtained in the same manner as above,

(ii) Production and Evaluation of Pattern (EB)

The positive resist solution prepared above was uniformly coated on a hexamethyldisilazane-treated silicon wafer by using a spin coater and dried under heating at 120° C. for 90 seconds to form a positive resist film having a thickness of 0.15 μm. This resist film was then irradiated with electron beams by using an electron beam image-drawing apparatus (HL750, manufactured by Hitachi Ltd., accelerating voltage: 50 KeV). After the irradiation, the resist film was baked at 110° C. for 90 seconds, dipped in an aqueous 2.38 mass % tetramethylammonium hydroxide (TMAH) solution for 60 seconds, rinsed with water for 30 seconds and dried. The obtained pattern was evaluated by the following methods.

[Sensitivity]

The cross-sectional profile of the pattern obtained was observed using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.). The minimum irradiation energy when resolving a 150-nm line (line:space=1:1) was defined as the sensitivity.

[Resolution]

The line size (line:space=1:1) when despite partial occurrence of pattern collapse, the line and space were separated and resolved with the irradiation dose giving the sensitivity above, was called a critical resolving size and defined as the resolution.

[Line Edge Roughness (LER)]

With respect to the region of 50 μm-edge in the longitudinal direction of a 150-nm line pattern at the irradiation dose giving the sensitivity above, the distance from a reference line where the edge should be present was measured at arbitrary 30 points by a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.). Based on the results, the standard deviation was determined, and 3σ was calculated. As the value is smaller, the performance is better.

[Dimension Before Collapse]

The line size (line:space=1:1) when the line and space were separated and resolved with the irradiation dose giving the sensitivity above while not causing pattern collapse at all was defined as the dimension before collapse and used as an index for the suppression of collapse. As the value is smaller, the performance is better.

TABLE 2 Component Acid Component Basic Dimension B Generator A Compound Surfactant Solvent Sensitivity Resolution LER Before Collapse Example (1.255 g) (0.0759 g) (0.02 g) (g) (0.002 g) (mass ratio) (μC/cm²) (nm) (nm) (nm) 1 RA-1 z17 A-38 none W-4 S-1/S-2 10 75 6.1 87.5 (8/2) 2 RA-2 z4 A-43 none W-3 S-1/S-3 10 62.5 6.2 75 (6/4) 3 RA-3 z4 A-8 none W-3 S-1/S-4 10 62.5 6.3 75 (6/4) 4 RA-4 z65 A-9 N-3 W-3 S-1/S-4 10 62.5 6.4 75 (0.01 g) (0.002 g) (8/2) 5 RA-5 z4 A-8 none W-4 S-1/S-2 11 62.5 6.4 75 (8/2) 6 RA-6 z17 A-21 none W-3 S-1/S-3 10 75 6.4 87.5 (6/4) 7 RA-7 z4 A-16 none W-3 S-1/S-4 10 62.5 6.4 75 (8/2) 8 RA-8 z4 A-38 none W-4 S-1/S-2 10 75 6.4 75 (8/2) 9 RA-9 z4 A-43 none W-3 S-1/S-3 10 75 6.4 75 (6/4) 10 RA-10 z66 A-21 none W-3 S-1/S-4 10 75 6.4 87.5 (8/2) 11 RA-11 z17 A-16 none W-4 S-1/S-2 11 62.5 6.4 75 (8/2) 12 RA-12 z4 A-38 none W-3 S-1/S-3 10 62.5 6.4 75 (6/4) 13 RA-13 z4 A-21 none W-3 S-1/S-4 10 62.5 6.4 75 (8/2) 14 RA-14 z5 A-22 none W-3 S-1/S-4 11 62.5 6.4 75 (8/2) 15 RA-15 z30 A-9 N-1 W-4 S-1/S-2 11 62.5 6.4 75 (0.01 g) (0.002 g) (8/2) 16 RA-16 z4 A-21 none W-3 S-1/S-3 11 75 6.4 87.5 (6/4) 17 RA-17 z4 A-16 none W-3 S-1/S-4 11 75 6.7 87.5 (8/2) 18 RA-18 z55 A-8 none W-3 S-1/S-2 10 62.5 6.4 75 (8/2) 19 RA-19 z2 A-21 none W-1 S-1/S-3 10 75 6.3 87.5 (6/4) 20 RA-20 z66 A-16 none W-1 S-1/S-4 11 75 6.4 87.5 (8/2) 21 RA-21 z4 A-16 none W-4 S-1/S-2 10 62.5 6.4 75 (8/2) 22 RA-22 z4 A-21 none W-3 S-1/S-3 10 75 6.3 87.5 (6/4) 23 RA-23 z4 A-8 none W-3 S-1/S-4 11 75 6.3 87.5 (8/2) 24 RA-24 z5 A-9 none W-4 S-1/S-4 10 75 6.4 87.5 (8/2) 25 RA-25 z55 A-9 N-2 W-3 S-1/S-2 10 75 6.4 87.5 (0.01 g) (0.002 g) (8/2) 26 RA-26 z2 A-16 none W-1 S-1/S-3 11 62.5 6.5 75 (6/4) 27 RA-27 z66 A-38 none W-1 S-1/S-4 10 62.5 6.5 75 (8/2) 28 RA-28 z66 A-43 none W-1 S-1/S-4 10 62.5 6.5 75 (8/2) 29 RA-29 z55 A-21 none W-3 S-1/S4 10 75 6.7 87.5 (8/2) 30 RA-6 z4 A-1 none W-3 S-1/S-2 10 75 6.7 87.5 (0.01 g) (8/2) A-20 (0.01 g) 31 RA-24 z4 A-1 N-1 W-1 S-1/S-2 10 75 6.7 87.5 (0.005 g) (0.002 g) (8/2) A-20 (0.005 g)

TABLE 3 Dimension Basic Before Comparative Resin Acid Generator Component A Compound Surfactant Solvent Sensitivity Resolution LER Collapse Example (1.255 g) (0.0759 g) (0.02 g) (0.004 g) (0.002 g) (mass ratio) (μC/cm²) (nm) (nm) (nm) 1 RA-1 z17 none N-3 W-4 S-1/S-2 15 100 95 125 (8/2) 2 RA-9 z4 none N-1 W-3 S-1/S-3 16 100 9 125 (6/4) 3 RA-16 z4 none N-2 W-3 S-1/S-3 14 100 6.4 125 (6/4) 4 RA-23 z4 none N-2 W-3 S-1/S-4 15 100 63 125 (8/2) 5 RA-29 z55 none N-1 W-3 S-1/S-2 15 100 6.7 125 (8/2) 6 T-1 z55 none N-1 W-3 S-1/S-2 14 87.5 7.5 200 (8/2) 7 T-2 z4 none N-1 W-3 S-1/S-2 14 87.5 7.6 200 (8/2) Abbreviations used in Tables 2 and 3 are shown below. <Resin >

(T-1)

(T-2) Basic Compound: N-1: Trio etylamine N-2: 1,5-Diazabicyclo[4.3.0]-5-nonene N-3: 2,4,6-Triphenylimidazole Surfactant: W-1: Megafac P176 (produced by Dainippon Ink & Chemicals, Inc.) W-2: Megafac R08 (produced by Dainippon Ink & Chemicals, Inc.) W-3: Troysol S-366 (produced by Troy Chemical) W-4: Polyoxyethylene lauryl ether Solvent: S-1: Propylene glycol monomethyl ether acezate S-2: Propylene glycol monomethyl ether S-3: Ethyl lactate S-4: Cyclohexanone

It is seen from Tables 2 and 3 that the resist composition of the present invention is excellent in all performances of sensitivity, resolution and LER as compared with the resist compositions of Comparative Examples.

Using the resist composition in each of Examples 1 to 8 and 13 to 15 and Comparative Examples 1 and 2, a resist film was obtained in the same manner as in Example 1. The obtained resist film was subjected to surface exposure with EUV light (wavelength: 13.5 nm) by changing the exposure amount in steps of 0.5 mJ in the range from 0 to 20.0 mJ and baked at 110° C. for 90 seconds. Thereafter, the dissolution rate at each exposure amount was measured using an aqueous 2.38 mass % tetramethylammonium hydroxide solution to obtain a sensitivity curve. The exposure amount when the dissolution rate of the resist was saturated in the sensitivity curve above was defined as the sensitivity and also, the dissolution contrast (γ value) was calculated from the gradient in the straight line part of the sensitivity curve. As the γ value is larger, the dissolution contrast is more excellent. The results obtained are designated as the results of Examples 32 to 42 and Comparative Examples 8 and 9, respectively.

The evaluation results are shown in Table 4.

TABLE 4 Sensitivity (mJ/cm²) γ Value Example 32 9 7.9 33 9 8.6 34 9 7.9 35 9.5 8.6 36 10 8.7 37 9.5 8.4 38 9 8.4 39 9.5 8.6 40 9 8.4 41 10 8.4 42 10 8.7 Comparative 8 15.5 6.8 Example 9 17 7.0

It is seen from the results of Table 4 that the composition of the present invention exhibits good sensitivity and good dissolution contrast even in the EUV exposure.

This application is based on Japanese Patent application JP 2006-264821, filed Sep. 28, 2006, the entire content of which is hereby incorporated by reference, the same as if fully set forth herein.

Although the invention has been described above in relation to preferred thereof, it will be understood by those skilled in the art that other variations and modifications can be effected in these preferred embodiments without departing from the scope and spirit of the invention. 

1. A resist composition comprising: a polymer having a group capable of decomposing under an action of an acid and having a weight average molecular weight of from 1,500 to 4,000, of which solubility in an alkali developer increases under an action of an acid; and a compound capable of generating a compound having a structure represented by the following formula (A-II) upon irradiation with actinic rays or radiation: Q₁-X₁—NH—X₂-A-(X₃)_(n)—B-Q₃  (A-II) wherein Q₁ and Q₃ each independently represents a monovalent organic group, provided that either one of Q₁ and Q₃ has a proton acceptor functional group, Q₁ and Q₃ may be combined with each other to form a ring and the ring formed may have a proton acceptor functional group; X₁, X₂ and X₃ each independently represents —CO— or —SO₂—; A represents a divalent linking group; B represents a single bond, an oxygen atom or —N(Q_(x))-; Q_(x) represents a hydrogen atom or a monovalent organic group; when B is —N(Q_(x))-, Q3 and Q_(X) may be combined with each other to form a ring; and n represents 0 or 1; wherein the polymer having a group capable of decomposing under an action of an acid comprises a repeating unit represented by the following formula (II) and a repeating unit represented by the following formula (III):

wherein each R₀₁ independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, L₁ and L₂, which may be the same or different, each represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aralkyl group, M represents a single bond or a divalent linking group, Q represents an alkyl group, a cycloalkyl group or an alicyclic or aromatic ring group which may contain a heteroatom, at least two members out of Q, M and L₁ may combine to form a 5- or 6-membered ring, A represents a cyano group, an acyl group, an alkoxy group, an acyloxy group or an alkoxycarbonyl group, and m and n each independently represents an integer of 0 to 4, provided that at least one of m and n is not
 0. 2. The resist composition as claimed in claim 1, which comprises a compound capable of generating an acid upon irradiation with actinic rays or radiation.
 3. The resist composition as claimed in claim 1, further comprising a nitrogen-containing basic compound.
 4. The resist composition as claimed in claim 1, further comprising a surfactant.
 5. The resist composition as claimed in claim 4, wherein the surfactant contains at least one of a fluorine atom and a silicon atom.
 6. A pattern forming method comprising: forming a resist film from the resist composition claimed in claim 1; and exposing and developing the resist film.
 7. The resist composition as claimed in claim 1, wherein the polymer having a group capable of decomposing under an action of an acid further comprises a repeating unit represented by the following formula (IV):

wherein each R₀₁ independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, B represents a halogen atom, a cyano group, an acyl group, an alkyl group, an alkoxy group, an acyloxy group or an alkoxycarbonyl group, and p represents an integer of 0 to
 5. 8. The resist composition as claimed in claim 1 wherein A in the formulae (II) and (III) is an acyl group, an acyloxy group or an alkoxycarbonyl group. 